international symposium on advanced green catalysis and...

1

International Symposium on Advanced Green Catalysis and Materials

Time Symposium Session Nov. 18th (Tue) Symposium Session

Nov. 19th (Wed)

Chair Prof. Chien-Tien Chen (NTNU)

09:30-10:00 Prof. Naoto Chatani (Osaka U.)

10:00-10:30 Prof. Chien-Hong Cheng (NTHU)

10:30-11:00 Coffee break

Chair Prof. Ken-Tsong Wong (NTU)

11:00-11:30 Prof. Masahiko Yamaguchi (Tohoku U.)

11:30-12:00 Registration and check in

Prof. Chien-Tien Chen (NTNU)

12:00-13:30 Lunch

13:30-14:20 reception Coffee break

Chair Prof. Ming-Chang Yeh (NTNU) Prof. Ming-Chang Yeh (NTNU)

14:20-14:50 Prof. Biing-Jiun Uang (NTHU) Prof. Fumitoshi Kakiuchi (Keio U.)

14:50-15:20 Prof. Takahiko Akiyama (Gakushuin) Prof. Yi-Chou Tsai (NTHU)

15:20-15:50 Prof. Junji Inanaga (Kyushu U.) Prof. Tohru Yamada (Keio University)


Chair Prof. Biing-Jiun Uang (NTHU) Prof. Yi-Chou Tsai (NTHU)

16:10-16:40 Prof. Michinori Suginome (Kyoto U.) Prof. Shigeru Yamago (Kyoto U.)

16:40-17:10 Prof. Han-Mou Gau (NCHU) Prof. Shigehiro Yamaguchi (Nagoya U.)

17:10-17:40 Prof. Toshikazu Hirao (Osaka U.) Prof. Tien-Yau Luh (NTU)

18:30-20:30 Dinner Dinner (Grand hotel)

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International Symposium on Advanced Green Catalysis and Materials

Program November 18, 2008 (Tuesday)

11:00-12:00 Registration and check in

12:00-13:30 Lunch

13:30-14:20 Reception

Chairman Prof. Ming-Chang Yeh (NTNU)

14:20-14:50 Enantioselective C-C Bond Formation Usingn New Camphor Derived Chiral Catalysts

Prof. Biing-Jiun Uang Department of Chemistry, National Tsing Hua University Hsinchu, Taiwan

14:50-15:20 Niobium-Catalyzed Intramolecular Coupling Reactions of Carbon-Fluorine Bonds and sp2- Carbon-Hydrogen Bonds

Prof. Takahiko Akiyama Department of Chemistry, Faculty of Science,Gakushuin, Japan

15:20-15:50 Heterogeneous Catalysis with Reusable Rare Earth Coordination Polymers

Prof. Junji Inanaga Institute for Materials Chemistry and Engineering Kyushu University,Japan


Chairman Prof. Biing-Jiun Uang (NTHU)

16:10-16:40 Helical Polyquinoxalines as New Scaffold for Chiral Polymer Catalysts in Catalytic Asymmetric Reactions

Prof. Michinori Suginome Department of Synthetic Chemistry and Biological Chemistry, Graduate

School of Engineering, Kyoto University, Japan

16:40-17:10 Synthesis and Structures of Organoaluminum Reagents and Their Applications to Asymmetric Catalytic Addition Reactions to Organic Carbonyls Prof. Han-Mou Gau Department of Chemistry, National Chung Hsing University, Taichung, Taiwan

3

17:10-17:40 Organic Synthesis via Vanadium Redox Prof. Toshikazu Hirao Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Japan

18:30-20:30 Dinner

November 19, 2008 (Wednesday)

Chairman Prof. Chien-Tien Chen (NTNU)

09:30-10:00 Nickel-Catalyzed Miyaura-Suzuki Type Coupling Reaction of Anisoles Professor Naoto Chatani Department of Applied Chemistry, Faculty of Engineering, Osaka University, Japan

10:00-10:30 Isoquinolinium Salts from ortho-Halobenzaldehyde Imines and Alkynes Catalyzed by Nickel Complexes: An Efficient Method for the Synthesis of Benzo[c]phenanthridine Alkaloids

Professor Chien-Hong Cheng Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan


Chairman Prof. Ken-Tsong Wong (NTU)

11:00-11:30 Rhodium-Catalyzed Synthesis of Organosulfur and Organophosphorous Compounds

Prof. Masahiko Yamaguchi Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences,†WPI Advanced Institute for Materials Research, Tohoku University, Japan

11:30-12:00 Doubly Ortho-linked Quinoxaline/Spirofluorene and cis-4,4’-Bis (diarylamino)stilbene/Fluorene Hybrids as Fluorescent Materials for Optoelectronic Applications

Prof. Chien-Tien Chen Department of Chemistry, National Taiwan Normal University, Taipei,

Taiwan

12:00-13:30 Lunch


4

Chairman Prof. Ming-Chang Yeh (NTNU)

14:20-14:50 Ruthenium-Catalyzed Cross-Coupling Reactions of Aromatic Ketones with Organoboronates via Aryl Carbon-Oxygen and -Nitrogen Bonds Cleavage

Prof. Fumitoshi Kakiuchi Department of ChemistryFaculty of Science and Technology, Keio University, Japan

14:50-15:20 Quintuply-Bonded Dichromium Complexes: Syntheses, Characterizations, and Reactivity

Prof. Yi-Chou Tsai Department of Chemistry, National Tsing Hua Univerity, Hsinchu, 30013 Taiwan

15:20-15:50 Cobalt-Catalyzed Oxidative Kinetic Resolution of Secondary Alcohols with Molecular Oxygen Prof. Tohru Yamada Department of Chemistry, Keio University, Japan


Chairman Prof. Yi-Chou Tsai (NTHU)

16:10-16:40 Organotellurium Mediated Living Radical Polymerization Initiated by Direct C-Te Bond Photolysis Prof. Shigeru Yamago Institute for Chemical Research, Kyoto University, Japan

16:40-17:10 Several Types of Intramolecular Double Cyclization from o,o'-Disubstituted Diphenylacetylenes Prof. Shigehiro Yamaguchi Department of Chemistry, Graduate School of Science, Nagoya University, Japan

17:10-17:40 Symmetry Breaking in Centrosymmetric Cyclophandienes Prof. Tien-Yau Luh Department of Chemistry, National Taiwan University

18:30-20:30 Dinner

5

Enantioselective C-C Bond Formation Usingn New Camphor Derived Chiral Catalysts

Hsyueh-Liang Wu, Ping-Yu Wu, Biing-Jiun Uang* Department of Chemistry, National Tsing Hua University Hsinchu, Taiwan 30013

[email protected]

Chiral alcohols are important compounds that

either show biological activity or are key intermediates for natural product synthesis. The design of novel reactions that proceed with high atom economy and enable multiple transformations through a shorter reaction sequence is an integral part of modern organic synthesis. Utility of chiral ligands in catalytic enantioselective C-C bond formation is amply demonstrated in a myriad of organic

transformations. Over the past two decades organozinc chemistry

has been developed into an important component of the organic synthesis addressing the aforementioned goals in an elegant manner. We report our findings in the enantioselective addition of organozinc reagents to aldehydes in the presence of a catalytic amount of camphor derived chiral ligands.

R1CHO + MeZn

R2

R31 (10 mol %)

−30 oC, 20 hR1

R2

R3

OH

95 - >99.5% ee75 - 91% yield

SH

NO

1

R4CHO + HR5

20 mol % Zn(OTf)220 mol % 1

50 mol % TEAtoluene, 50 oC

R4R5

OH

64 - >97% ee35 - 97% yield

1.Uang, B.-J.; Fu, I-P.; Hwang, C.-D.; Chang, C.-W.; Yang, C.-T.; Hwang, D.-R. Tetrahedron

(Symposium-in-Print) 2004, 60, 10479. 2. Wu, P.-Y.; Wu, H.-L.; Uang, B.-J. J. Org. Chem. 2006, 71, 833. 3. Wu, H.-L.; Wu, P.-Y.; Uang, B.-J. J. Org. Chem. 2007, 72, 5935. 4. Wu, P.-Y.; Wu, H.-L.; Shen, Y.-Y.; Uang, B.-J. J. Org. Chem. 2008, 73, 6445.

Biing-Jiun Uang, b 1953 in Taipei, Taiwan. Tamkang Univ. (B 1975), National Tsing Hua Univ. (MS 1979), Yale Univ. (Ph. D., with Prof. S. D. Danishefsky). Postdoc. California Institute of Technology (with Prof. R. E. Ireland). Associate Prof. (1985-90), Prof., (1990-present), Chairman (Aug. 2003- Jul. 2006), Chemistry Department, National Tsing Hua Univ. Director (Oct. 2006- ), Instrumentation Center, National Tsing Hua University. Research interest: asymmetric synthesis, asymmetric catalysis, natural product synthesis, bioorganic chemistry, medicinal chemistry.

6

Niobium-Catalyzed Intramolecular Coupling Reactions of Carbon-Fluorine Bonds and sp2- Carbon-Hydrogen Bonds

Takahiko Akiyama

Department of Chemistry, Faculty of Science, Gakushuin University, Tokyo, Japan;

[email protected]

Activation of carbon-fluorine bonds and carbon-hydrogen bonds is one of the most important objectives in synthetic organic chemistry. We have found that low-valent niobium, which is generated in situ from NbCl5 and LiAlH4, is an efficient catalyst for the activation of the C-F bonds. Hydrodefluorination of fluorobenzene derivatives proceeded smoothly under the influence of NbCl5 (5 mol%) and LiAlH4 (2 equiv) in DMF to give benzene derivatives in high yields (Scheme 1).1

FAr

HAr

NbCl5 (5 mol%)LiAlH4 (2 equiv)

DME, 85 ÞC, 2-8 h

(1)

Trifluorotoluene derivatives also underwent hydrodefluorination by means of NbCl5-LiAlH4 to give toluene derivatives in high yields (Scheme 2).2

CF3Ar

CH3Ar


DME, reflux 4-10 h

(2)

During the study, we have found that the low-valent niobium is an efficient catalyst for intramolecul

ar coupling reactions of the C-F bonds and the sp2 C-H bonds. o-Aryl- and o-alkenyl-α,α,α-trifluorotoluene derivatives were treated with 30 mol% of NbCl5 and excess amounts of LiAlH4. The reaction mixture was refluxed for several hours and quenched with water. The CF3 groups underwent coupling reactions with the neighboring sp2-C-H bonds, and fluorene and indene derivatives were obtained in good yields, respectively. C-O, C-N, C-S, and aromatic C-F bonds were tolerant to the reaction conditions, and the corresponding hetero atom-subsituted products were obtained in good yields (Scheme 3).3

CF3

R1 R1

R2 R2


dioxane, reflux 2-6 h

(3)

Transition metal-catalyzed coupling reactions of organofluorine compounds with organometallic reagents have been reported in recent years. We could develop coupling reactions of the CF3 groups with the non-activated sp2 C-H bonds for the first time.

1. Fuchibe, K.; Akiyama, T. Synlett 2004, 1282-1284. 2. Fuchibe, K.; Ohshima, Y.; Mitomi, K.; Akiyama, T. Org. Lett. 2007, 9, 1497-1499. Fuchibe, K.; Ohshima, Y.; Mitomi,

K.; Akiyama, T. J. Fluorine Chem. 2007, 128, 1158-1167. 3. Fuchibe, K.; Akiyama, T. J. Am. Chem. Soc. 2006, 128, 1434-1435. Fuchibe, K.; Mitomi, K.; Suzuki, R.; Akiyama, T.

Chem. Asian J. 2008, 3, 261-271. Takahiko Akiyama, b 1958 in Okayama, Japan. The Univ. of Tokyo (BS 1980); The University of Tokyo (MS 1982); The University of Tokyo (PhD 1985, Prof. T. Mukaiyama), Shionogi Res. Lab. (1985-1988); Assistant Prof. (1988, Ehime Univ); Stanford Univ. (visiting scholar. 1992, Prof. B. M. Trost). Associate Prof. (1994, Gakushuin Univ.); Prof. (1997-, Gakushuin Univ.). Research interest: development of new organocatalyzed and metal-catalyzed reactions

7

Heterogeneous Catalysis with Reusable Rare Earth Coordination Polymers

Junji Inanaga

Institute for Materials Chemistry and Engineering (IMCE), Kyushu University;

Fukuoka 812-8581, Japan; [email protected]

The development of high-performance and reusable solid catalysts is of current interest in the context of green-sustainable chemistry and technology. Recently, we succeeded in preparing a new class of self-organized chiral and porous polymeric lanthanum complex catalysts, which have chiral ligands [(R)-BINOL units] connected with appropriate multi-way spacers consisted with sp and/or sp2 carbons, and they could be utilized as a storable and reusable heterogeneous catalyst for the highly enantioselective epoxidation of conjugated enones (up to >99% ee).1 The catalyst system could also be successfully used for the micro flow reaction, in which ca. 1 mol% of the catalyst was employed and the desired epoxide with 99% ee was obtained in >93% yield (TON

>100).2 We have also succeeded in preparing novel rare earth coordination polymer Lewis acid catalysts from rare earth triisopropoxides and multidentate sulfonate ligands in one step. The corresponding Sc-CP catalysts were found to be particularly effective for the ring-opening reaction of cyclohexene oxide with benzylamine under solvent-free heterogeneous conditions to give the corresponding 　-amino alcohol in quantitative yield.3 The catalysts are highly practical since they can be stored at ambient temperature without any special care, quantitatively recovered after the reaction, and reused many times (more than ten times) without losing their activities.

1. Inanaga, J.; Hayano, T.; Furuno, H. Shokubai, 45, 285 (2003). 2. Onitsuka, S.; Kalluri. V. S. Ranganath; Furuno, H.; Inanaga, J. unpublished result. 3. Ishida, S.; Suzuki, S.; Hayano, T.; Furuno, H.; Inanaga, J. J. Alloys Compd., 408-412, 441 (2006).

Junji Inanaga, Kyushu University (BS 1970; Ph.D. 1975), Assistant Prof. (1975), Associate Prof. (Institute for Molecular Science, 1989), Professor (Kyushu Univ., 2000-). Post-doc (Indiana Univ., 1981-1983), Guest Professorships (Universite Paris-Sud, 1994; Kyoto Univ., 1996; Hobei Univ., 2005-). Research field: synthetic study of natural products (carotenoids, macrolides, quassinoids, etc.), new synthetic methods (SmI2 chem., etc.), chiral recognition, and asymmetric catalysis. President of the Rare Earth Society of Japan, 2006-.

8

Helical Polyquinoxalines as New Scaffold for Chiral Polymer Catalysts in Catalytic Asymmetric Reactions

Takeshi Yamamoto and Michinori Suginome

Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering,

Kyoto University, Katsura, Kyoto 615-8510, Japan; [email protected]

Recent progress in asymmetric polymer synthesis has

enabled the selective construction of unnatural

macromolecular architectures whose main chains

adopt nonracemic helical structures. Employment of

such chiral macromolecular structures for chiral

reaction environment, however, has not been very

successful. For use of chiral macromolecules in

asymmetric catalysis, their scaffolds have to be highly

enantiopure, highly robust, and highly modifiable for

the introduction of reaction sites to their side chains.

�We herein report highly enantioselective catalytic

reactions that took place on the palladium atom

attached to asymmetrically synthesized single-handed

helical polymers. Optically active, helical

poly(quinoxaline-2,3-diyl) bearing diarylphosphino

groups at their side chains was prepared by living

block co-polymerization of 1,2-diisocyanobenzene

derivatives. A single-handed helix (>90% s.e.) was

induced by using optically active organopalladium

complex as a chiral initiator. The optically active

block co-polymer was utilized as a chiral ligand on

palladium in catalytic asymmetric hydrosilylation of

styrene derivatives. Using 0.1 mol% of a palladium

complex with 0.2 mol% of the polymer ligand, up to

87% ee was attained.

N

N

N

NN

N

NN

N

N

NN

N

NPPh2

N

N

SAr*

H

PrO

PrO

OPr

OPr

OPr

OPr

OPr

OPrPrO

PrO

Pd(0)

HSiCl3 +

R

RSiCl3

up to 87% ee

Catalyst TON ~ 1000

SArPdI(PMe2Ph)

NC

NC

PrO

Me

Me

PrO NC

NCMe

P(O)Ph2

10 equiv 1 equiv

NC

NC

PrO

Me

Me

PrO

10 equiv

> 90% right-handed helix

Michinori Suginome, b 1966 in Sapporo, Japan. Kyoto Univ. (BS 1988; MS 1990; Ph.D. 1993,

Prof. Y. Ito), Kyoto Univ. Assistant Prof. (1993), Associate Prof. (2002), Professor (2004-). MIT

Visiting Researcher (1998-1999, Prof. G. C. Fu). Research filed: organic synthesis,

organosilicon and organoboron chemistry, transition metal catalysis, and polymer synthesis

9

Synthesis and Structures of Organoaluminum Reagents and Their Applications to Asymmetric Catalytic Addition Reactions to Organic Carbonyls

Kuo-Hui Wu, Da-Wei Chuang, Shuangliu Zhou, Deepak B Biradar

and Han-Mou Gau*

Department of Chemistry, National Chung Hsing University, Taichung, Taiwan, ROC

email: [email protected]

A series of AlArxEt3-x(L) was synthesized and characterized. Molecular structures of AlPh3(L) (L = OEt2, THF, OPPh3, or DMAP (4-dimethylamino- pyridine)) and AlPh2Et(DMAP) were determined. Additions of AlPh3(L) to 1-naphthylaldehyde catalyzed by the titanium catalyst of (R)-H8-BINOL revealed that the adduct L ligands have a strong effect on yields and enantioselectivities of the addition product, and only the AlPh3(THF) reagent afforded the desired secondary alcohol in excellent enantioselectivity of 98% ee. The addition of atomic efficient AlArEt2(THF) to aldehydes were studied, and arylation products were obtained exclusively or as major products with excellent enantioselectivities. Depending on substrates, ethylation products were also observed with yields up to 29%. In contrast, additions of AlArEt2(THF) to ketones catalyzed by

the titanium catalyst of (S)-BINOL afforded only aryl addition products with enantioselectivities up to 94% ee.

The titanium catalyst of (S)-BINOL also applied to additions of Al(2-furyl)Et2(THF) to ketones, furnishing chiral tertiary 2-furyl alcohols in high yields and enantioselectivities from 87 to 93% ee. Chiral 2-furyl alcohols are key intermediates which can be converted into a wide variety of bioactive compounds.

Asymmetric vinyl additions to ketones catalyzed by the titanium catalyst of (S)-BINOL were studied employing in situ prepared vinylaluminum reagents from reactions of terminal alkynes with DIBAL-H, and the vinylation reactions produced chiral tertiary allylic alcohols in good yields and excellent enantioselectivities up to 97% ee.

OHOH

OHOH

R1 R2

O

R1 R2

OH

R3

(S)-BINOL

+ AlR3xEt3-x(THF)

L* =

L*/Ti(OiPr)4

or

(R)-H8-BINOL

R1 = alkyl or arylR2 = H or alkyl

R3 = Ar,

O

R4, or

x = 1 or 3

Han-Mou Gau b. 1954 in Taipei, Taiwan. National Chung Hsing University(BS, 1977), Cornell University (MS, 1984; Ph.D. 1987). Associate Professor (1987-1993), Professor (1993-). Research field: organometallic reagents, asymmetric catalysis,coupling reactions.

10

Organic Synthesis via Vanadium Redox

Toshikazu Hirao, Toshiyuki Moriuchi, Toru Amaya, Kotaro Kikushima, and Yusuke Tsukamura

Department of Applied Chemistry, Graduate School of Engineering, Osaka University,

Yamada-oka, Suita, Osaka 565-0871, Japan, [email protected]

A redox process of vanadium compounds via

one-electron oxidation or reduction is envisioned to provide various synthetic tools in organic synthesis.1 Two new oxidative transformations are described here.

The oxidative coupling of nucleophiles is considered to be a complementary method for the conventional nucleophile-electrophile coupling. We have previously reported the selective carbon-carbon bond formation of main-group organometallics, such as organoaluminiums,2 organoborons,3 organozincs,4 and their ate complexes using oxovanadium(V) compounds as a stoichiometric oxidant. The vanadium(V)- catalyzed oxidative ligand coupling of various tetrasubstituted borates is possible by the recycle of the active vanadium species under oxygen.

Sodium tetraarylborates are treated with 20 mol% VO(OEt)Cl2 under atmospheric oxygen to give the corresponding symmetrical biaryls.5 The ligand coupling for the unsymmetrical biaryls is also achieved with the borates prepared from aryllithiums and triphenylboron in situ.

Bromination is one of the most important reactions

in organic synthesis, providing versatile precursors and substrates in various coupling reactions as

mentioned above. Conventional bromination, however, involves the use of highly toxic bromine. To avoid the use of bromine, an alternative bromination method is required. An efficient bromination reaction by using NH4VO3 as a catalyst combined with H2O2, KBr, and HBr in an aqueous media under relatively mild conditions is developed in our laboratory, mimicking the catalytic activity of vanadium bromoperoxidase (VBrPO).6 In this method, a bromonium cation-like species is considered to be generated by two-electron oxidation of a bromide ion.

More importantly, the NH4VO3-catalyzed oxidative bromination was found to be achieved by the reaction under oxygen, providing an environmentally-favorable bromination system.

The bromination reaction of 1,3,5-trimethoxy- benzene in the presence of 5 mol% of NH4VO3, 300 mol% of tetrabutylammonium bromide and trifluoroacetic acid under atmospheric oxygen gives the monobromo compound in 80% yield. This bromination system could be applied to the bromination of arenes, alkenes, and alkyne.

1. Hirao, T. Chem. Rev. 1997, 97, 2707. 2. Ishikawa, T.; Ogawa, A.; Hirao, T. J. Am. Chem. Soc. 1998, 120, 5124. 3. Ishikawa, T.; Nonaka, S.; Ogawa, A.; Hirao, T. Chem. Commun. 1998, 1209. 4. Hirao, T.; Takada, T.; Ogawa, A. J. Org. Chem. 2000, 65. 1511; Hirao, T.; Takada, T.; Sakurai, H. Org. Lett. 2000, 2, 3659.

5. Mizuno, H.; Sakurai, H.; Amaya, T.; Hirao, T. Chem. Commun. 2006, 5042. 6. Moriuchi, T.; Yamaguchi, M.; Kikushima, K.; Hirao, T. Tetrahedron Lett. 2007, 48, 2667.

Toshikazu Hirao, b 1949 in Osaka, Japan. Kyoto Univ. (BS 1973); Kyoto Univ. (Ph.D. 1978); Assistant Prof. at Osaka Univ. (1978); Postdoc. at Univ. of Wisconsin (1981-1982, Prof. Barry M. Trost); Associate Prof. (1992); Prof. (1994-). Research field: organic chemistry, organometallic chemistry, bioorganometallic chemistry, polymer chemistry.

MeO

OMe

OMe

NH4VO3Bu4NBrCF3COOH

1,4-dioxane, O2, 80 ºC, 18 h

5 mol%300 mol%300 mol%

MeO OMe

Br

Br

1) n-BuLi2) Ph3B

RBPh3

R

-

Li+O2 Ph

RVO(OEt)Cl2Ar

11

Nickel-Catalyzed Miyaura-Suzuki Type Coupling Reaction of Anisoles

Naoto Chatani

Department of Applied Chemistry, Faculty of Engineering, Osaka University; Suita, Osaka 565-0871, Japan;

[email protected]

Palladium- and nickel-catalyzed cross- coupling

reactions have been recognized as an indispensable

tool for current organic synthesis. Among these

reactions, the Suzuki-Miyaura cross coupling is,

arguably, of the greatest practical importance of these

methods. Despite recent significant advances, the

electrophilic coupling partner for use in the

Suzuki-Miyaura coupling remains limited, for the

most part, to organic halides and sulfonates.[1,2] We

present herein a method by which nickel-catalyzed

cross-coupling of aryl methyl ethers with boronic

esters is achieved.[3] Aryl methyl ethers on fused

aromatic systems, such as naphthalene and

phenanthrene, and anisoles containing

electron-withdrawing groups can be coupled with a

wide range of boronic esters.

OMe PhPh B

O

O

CsF

10 mol% Ni(cod)240 mol% PCy3

toluene80 °C, 12 h(1.2 equiv.)

+

89%

[1] For the cross-coupling of aryl methyl ethers with Grignard reagents, see: Wenkert, E.; Michelotti, E. L.;

Swindell, S. C. J. Am. Chem. Soc. 1979, 101, 2246. Wenkert, E.; Michelotti, E. L.; Swindell, C. S.; Tingoli, M. J.

Org. Chem. 1984, 49, 4894. Dankwardt, J. W. Angew. Chem. Int. Ed. 2004, 43, 2428. Guan, B.-T.; Xiang, S.-K.;

Wu, T.; Sun, Z.-P.; Wang, B.-Q.; Zhao, K.-Q.; Shi, Z.-J. Chem. Commun. 2008, 1437.

[2] The cross-coupling of aryl methyl ethers with boronic esters that requires a chelation assistance has been

reported: Kakiuchi, F.; Usui, M.; Ueno, S.; Chatani, N.; Murai, S. J. Am. Chem. Soc. 2004, 126, 2706; Ueno, S.;

Mizushima, E.; Chatani, N.; Kakiuchi, F. J. Am. Chem. Soc. 2006, 128, 16516.

[3] Tobisu, M.; Shimasaki, T.; Chatani, N. Angew. Chem. Int. Ed. 2008, 47, 4866.

Naoto Chatani, b 1956 in Hyogo, Japan. Osaka Univ. (BS 1979; MS 1981; Ph.D. 1984, Profs.

N. Sonoda and S. Murai), The Institute of Scientific and Industrial, Osaka Univ. Assistant Prof.

(1984) (Prof. T. Hanafusa), Osaka Univ. Assistant Prof. (1988) (Prof. S. Murai), Osaka Univ.

Associate Prof. (1992), Osaka Univ. Professor (2002-). Research filed: catalysis.

12

Isoquinolinium Salts from ortho-Halobenzaldehyde Imines and Alkynes Catalyzed by Nickel Complexes: An Efficient Method for the Synthesis of Benzo[c]phenanthridine

Alkaloids

Chien-Hong Cheng, Rajendra Prasad Korivi and Yu-Chen Wu

Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan; [email protected]

Recently, we have developed an efficient synthetic method for the synthesis of 3,4-disubstituted

isoquinolines1 and isoquinolinium salts.2 By using this

nickel catalyzed transformation, we are able to

synthesize a large variety of isoquinolines members

by simply modifying the reaction conditions. Also the

method can be utilized in the synthesis of natural

products in a convenient fashion. Several

benzo[c]phenanthridine alkaloids were comfortably

synthesized in good yields. The mechanism and other

interesting features of this reactions will be displayed.

N

I

R1

R3R2+N

R2

R3

Cond.AN+

R2

R3

R1I-

Cond.B

A : NiBr2L2, Zn or Ni(0) B : Ni(0)

N

O

O

O

O

O

N

O

O

O

MeO

MeO

N

O

O

O

OO

oxynitidineoxyavicine oxysanguinarine

[1] Korivi, R. P.; Cheng, C. H. Org. Lett. 2005, 7, 5179. [2] Wu, G.; Rhiengold, A. L.; Geib, S. J.; Heck. R. F.

Organometallics 1987, 6, 1941.

Chien-Hong Cheng received his B.S. degree in chemistry from National Tsing University in 1971. He obtained his PhD from University of Rochester in 1978 and pursued postdoctoral

work in the same laboratory (1978-79). He joined the Department of Chemistry of National

Tsing Hua University, Hsinchu, Taiwan, as an Associate Professor (1979-84), where he

became a full Professor in 1984. He was a visiting scientist at the Department of Chemistry,

Princeton University (1984-85). He became the Chairman of Chemistry Department from

1990 to 93. He is currently the Director of Department of Natural Sciences National Science

Council, Taiwan. His research interests include new organic synthetic methods catalyzed by

organometallic compounds and organic materials in optoelectronics.

13

Rhodium-Catalyzed Synthesis of Organosulfur and Organophosphorus Compounds

Masahiko Yamaguchi＊†

Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, †WPI Advanced Institute for Materials Research, Tohoku University,

Aoba, Sendai 980-8577, Japan

Organoheteroatom compounds of phosphorus and sulfur are important in relation to the development of biologically active substances and materials. Conventional synthesis in general employed substitution reactions of organohalogen compounds with heteroatom reagents. It was considered that i) the addition reaction to unsaturated compounds; ii) the substitution reaction of C-H bond; iii) single bond metathesis would be more favorable, since the starting materials are readily available, and the reactions are atom-economical. Described here is the use of transition metal catalysis for such syntheses of organosulfur and organophosphorus compounds.

The reaction of triarylphosphine and 1-alkynes in the presence of rhodium or palladium complex and sulfonic acid gave alkenylphosphonium salts. The method was applicable to simple alkenes such as ethylene and propylene, and the anti-Markovnikov adducts were obtained.1 Rhdium catalysis method could be used for the synthesis of organosulfur compounds, and 1-alkynes were converted to 1-alkylthioalkynes by reacting with disulfides.2 Aryl fluorides were substituted with disulfide giving aryl sulfides.3 It was found that rhodium complexes catalyzed various single bond metathesis reaction containing S-S or P-P bond cleavage.

S S

S S

S

S S

S SSnS H

S

P S

C SN

P P

P

P P S

C C+ PPh3

C C

Rh, Pd cat

Ar SCO S

CO C S

1. M. Ariwasa, and M. Yamaguchi, J. Am. Chem. Soc. 2006, 128, 50.

2.M. Ariwasa, K. Fujimoto, S. Morinaka, and M. Yamaguchi, J. Am. Chem. Soc. 2005, 127, 12226.

3. M. Ariwasa, T. Suzuki, T. Ishikawa, and M. Yamaguchi, J. Am. Chem. Soc. 2008, in press.

Masahiko Yamaguchi, b 1954 in Fukuoka, Japan. The University of Tokyo (B 1977), The University of Tokyo (M 1979), The University of Tokyo (PhD 1982, Prof. Mukaiyama), Asso. Prof. Kyushu Inst. Tech. (1985), Asso. Prof. Tohoku Univ. (1991), Prof. Tohoku Univ. (1997-present), Postdoc. Yale Univ. (New Haven, Prof. S. Danishefsky, 1987-1988). Research field: organic chemistry, organometallic chemistry, synthetic methodology (main element, transition metal, heteroatom), helicenes, nano-organic chemistry, organic materials. [email protected]

14

Doubly Ortho-linked Quinoxaline/Spirofluorene and cis-4,4’-Bis(diarylamino)stilbene/Fluorene Hybrids as Fluorescent Materials for Optoelectronic

Applications

Chien-Tien Chen,* Chin-Sheng Lin, Y. Wei, Liang-Yu Lin, and Wei-San Chao

Department of Chemistry, National Taiwan Normal University, Taipei, Taiwan, ROC;


A conceptually different strategy by connecting the individual ortho-position of two phenyl rings in spirofluorene framework to the C2-C3 edge of quinoxaline has been developed. One major merit of this approach is the resultant 1:1 hybrid may function as a clipable central core to any functional appendages at the pendant N-center, both the C3,C6 positions at the spiro-fluorene unit, or the C5-C8 positions at the quinoxaline backbone. With judicious choices of the appendages, the resultant butterfly-shape optoelectronic, amorphous materials act as fluorescent

bipolar chameleons with tunable color chromacity all the way from blue, to green, to yellow, to red, which are not readily achievable for any compact, dipolar skeletons. In addition, hybrids bearing a central dibenzosuberene optoelectronic unit with functional C3 and C7, N,N-diarylamino appendages and spiro-fluorene junction act as blue fluorescent OLED materials. Sharp blue fluorescent (464 nm, 　　fwhm: 47-60 nm) OLED devices can thus be furnished with high 　ext of 7.9%, L20 of 2689 cd/m2, 　c of 13.6 (cd/A), and 　p of 8.2 (lm/W).

N

NX G

acceptordonor

G

GR

R X

X

G

G

M

M = IrG = NAr2, C6H4-GX = N, C-Ar

O O

NX

X

NN ArAr

ArAr NNAr

ArAr

Ar

Ar = Ph, 1-Np, C6H4-p-OMe

1. Chen, C.-T.; Lin, J.-S.; Moturu, M. V. R. K.; Lin, Y.-W.; Yi, W.; Tao, Y.-T.; Chien, C.-H. Chem. Commun. 2005, 3980.

2. Chen, C.-T.; Wei, Y.; Lin, J.-S.; Moturu, M. V. R. K.; Chao, W.-S.; Tao, Y.-T.; Chien, C.-H. J. Am. Chem. Soc. 2006, 128,

10992.

3. Wei, Y.; Chen, C.-T. J. Am. Chem. Soc. 2007, 129, 7478.

Chien-Tien Chen, b 1964 in Taipei, Taiwan. National Tsing-Hua Univ. (BS 1986; MS 1988), Univ. of Illinois at Urbana-Champaign (Ph.D. 1994, Prof. S. Denmark), Scripps Research Institute (Postdoc. 1995, Prof. B. Sharpless) Associate Prof. (1995), Professor (2000-). Research filed: (synergistic) asymmetric catalysis, organic optoelectronic materials and LC-based optical switches, DNA photocleavages, and nanoparticle-encapsulated dendritic probes, directed assembly for synergistic ion-specific transport E-mail address.

15

Ruthenium-Catalyzed Cross-Coupling Reactions of Aromatic Ketones with Organoboronates via Aryl Carbon-Oxygen and -Nitrogen Bonds Cleavage

Fumitoshi Kakiuchi

Department of Chemistry, Faculty of Science and Technology, Keio University, Yokohama, Japan;

[email protected]

Transition metal-catalyzed reactions involving cleavage of unreactive carbon bonds are highly intriguing, challenging research subjects in modern organic synthesis.1 We have developed ruthenium-catalyzed cross coupling reactions of aromatic ketones with organoboronates via carbon-hydrogen bond cleavage to give ortho arylation2 and alkenylation3 products in high yields. Recently, we have developed ruthenium-catalyzed cross couplings via aryl carbon-oxygen in aryl ethers4 and carbon–nitrogen bonds in aryl amines.5 In this paper, we report scope and limitations of these new cross coupling reactions and mechanistic studies by means of NMR experiments. When a reaction of 2’-methoxy-6’-methylacetophenone with 5,5-dimethyl-2-phenyl-[1,3,2]dioxaborinane (1) was carried out in refluxing toluene using RuH2(CO)(PPh3)3 (2) as a catalyst, phenylation of Ar-OMe bond took place efficiently (eq 1).4

O

OMe

OB

OPh+

0.02 mmolRuH2(CO)(PPh3)3 (2)

toluene o.5 mLreflux, 20 h

O

Ph0.5 mmol 1 0.6 mmol quant.

(1)

A variety of combination of aryl ethers such as 2’-phenoxypivalophenone, and organoboronates such

as aryl-, alkenyl- and alkylboronates can be used in this coupling reaction. The reaction of 2’-methylacetophenone with trimethylvinylsilane and 1 using 2 as a catalyst afforded C-H alkylation and C-O phenylation product in 93% yield (eq 2).

O

OMe

+2 0.04 mmoltoluene, 0.5 mLreflux, 6 h

O

Ph0.5 mmol 1 mmol 93%

(2)SiMe3 + 1

1 mmol

SiMe3

A similar cross coupling rection of aryl amines also took place via Ar-NMe2 bond cleavage. A reaction of 2’-N,N-dimethylamino-2,2-dimethyl-propiophenone with 1 in the presence of catalyst 2 under toluene refluxing conditions provided the corresponding C-N phenylation product in 91% yield (eq 3).

But

O

NMe2

OB

OPh+

2 0.02 mmoltoluene 0.5 mLreflux , 20 h

But

O

Ph0.5 mmol 1 0.6 mmol 91%

(3)

Relative reactivity of C-H and C-O bonds towards the ruthenium complex was examined using 2’-aryloxyacetophenone. The results of this reaction revealed that oxidative addition of C-H bond was kinetically favorable process and oxidative addition of C-O bond was thermodynamically favorable one.

1. Activation of Unreactive Bonds and Organic Synthesis; Murai, S., Ed.; Springer, Berlin, 1999. 2. Kakiuchi, F.; Kan, S.; Igi, K.; Chatani, N.; Murai, S. J. Am. Chem. Soc. 2003, 125, 1698-1699. Kakiuchi, F.;

Matsuura, Y.; Kan, S.; Chatani, N. J. Am. Chem. Soc. 2005, 127, 5936-5945. 3. Ueno, S.; Chatani, N.; Kakiuchi, F. J. Org. Chem. 2007, 72, 3600-3602. 4. Kakiuchi, F.; Usui, M.; Ueno, S.; Chatani, N.; Murai, S. J. Am. Chem. Soc. 2004, 126, 2706-2707.; Ueno, S.;

Mizushima, E.; Chatani, N.; Kakiuchi, F. J. Am. Chem. Soc. 2006, 128, 16516-16517. 5. Ueno, S.; Chatani, N.; Kakiuchi, F. J.Am.Chem. Soc. 2007, 129, 6098-6099.

Fumitoshi Kakiuchi, b 1965 in Hyogo, Japan. Osaka Univ. (BS 1988);Osaka Univ. (MS 1990); Osaka Univ. (PhD 1993, Prof. S. Murai), Univ. of Wisconsin (visiting student 1991 Prof. R. West); Harrvard Univ. (postdoc. 1996, Prof. E. N. Jacobsen). Assistant Prof. (1993, Osaka Univ); Associate Prof. (2000, Osaka Univ.); Prof. (2005-, Keio Univ.). Research interest: development of new transitionmetal-catalyzed reactions [email protected]

16

Quintuply-Bonded Dichromium Complexes: Syntheses, Characterizations, and Reactivity

Yi-Chou Tsai Department of Chemistry, National Tsing Hua Univerity, Hsinchu, 30013 Taiwan

In this report, the syntheses, characterizations, and reactivity of a series of quintuply-bonded dichromium(I) complexes supported by amidinates, [Cr2(μ-η2-ArNC(R)NAr)3]– and Cr2μ-η2-ArNC(R)NAr)2 will be presented. All these diamagnetic complexes were prepared from the reduction of Cr2Cl2(THF)2(μ-η2-ArNC(R)NAr)2 and CrCl2(THF)2(η2-ArNC(R)NAr), respectively, and fully characterized by multi-nuclear NMR spectroscopy, elemental analysis, and X-Ray crystallography. The most striking feature of these complexes is that they all exhibit a Cr-Cr bond length of 1.74 Å being the shortest

metal-metal bond lengths yet with. It is noteworthy that the Cr-Cr bond lengths in these complexes are independent of the steric bulk of the ancillary amidinato ligands. DFT (Density Functional Theory) calculations were also employed to elucidate to the quintuple bonding between two chromium centers in these complexes. Notably, not only do these low-coordinate dichromium(I) complexes possess extremely short Cr-Cr bond distances, but they display very interesting reactions towards small molecules and organic substrates

. References: 1. Kreisel, K. A.; Yap, G. P. A.; Dmitrenko, O.; Landis, C. R.; Theopold, K. H. J. Am. Chem. Soc. 2007, 129, 14162. 2. Tsai, Y.-C.; Hsu, C.-W.; Yu, J.-S. K.; Lee, G.-H.; Wang, Y.; Kuo, T.-S. Angew. Chem. Int. Ed. 2008, 47, 7250. 3. Noor, A.; Wagner, F. R.; Kempe, R. Angew. Chem. Int. Ed. 2008, 47, 7246. 4. Tsai, Y.-C.; Hsu, C.-W.; Yu, J.-S. K.; Yen, C.-H.; Lee, G.-H.; Wang, Y. Angew. Chem. Int. Ed. 2008, accepted.

Yi-Chou Tsai (born in Pingtung, Taiwan in 1969) obtained both his B.S. (1991) and M.S. (1994) from National Taiwan Normal University. He was awarded a Ph.D. degree in 2001 from Massachusetts Instituted of Technology under the supervision of Professor Christopher C. Cummins. He then moved to California Institute of Technology as a postdoctoral fellow with Professor Robert H. Grubbs. In 2003, he moved back to Taiwan and was appointed as an Assistant Professor and promoted to an Associate Professor in 2008 at current institute. His research interests encompass (1) new methods for inorganic synthesis, (2) the synthesis, isolation, and characterization of unusually reactive transition metal complexes of unique

design and construction, (3) the activation of ubiquitous small molecules, (4) the assembly of novel functional groups containing transition metals, and (5) the development of new reagents for organic synthesis.

17

Cobalt-Catalyzed Oxidative Kinetic Resolution of Secondary Alcohols with Molecular Oxygen

Tohru Yamada

Department of Chemistry, Keio University, Yokohama, Japan;

[email protected]

Molecular oxygen is an abundant and ubiquitous oxidant on the earth as well as a clean, safe and easily handled oxidant compared to peroxides or heavy-metal oxidants, although the stereoselective oxidation by molecular oxygen remains one of the most challenging research targets because of its high radical-like reactivity and consequent side-reactions. Much effort has been performed to develop reliable complex catalysts containing various transition-metals that would provide efficient and stereoselective aerobic oxidation systems. The oxidative kinetic resolution of racemic alcohols with molecular oxygen was reported to establish one of the most efficient methods to obtain enantiomerically enriched secondary alcohols. Two catalyst systems using palladium(II) complexes1 were independently reported. The vanadyl(V) carboxylate complexes with N-salicylidene2 and the (nitroso)(salen)-ruthenium(II)3 complexes have also been developed to perform the highly selective oxidative kinetic resolution of the α-hydroxy ester or amide and propargyl alcohols, respectively, using molecular oxygen as the oxidant. Very recently, it was reported that the ruthenium or iridium complex with a chiral bifunctional amido ligand effectively catalyzed the aerobic oxidative kinetic resolution of benzylic secondary alcohols.4 It has been noted that Schiff-base cobalt(II) complexes could capture and activate molecular oxygen, and various aerobic oxidation reactions

have been examined in the presence of these cobalt complexes. By using the bis(1,3-diketonato)cobalt(II) complexes as catalysts, various alkenes were converted into the corresponding alcohol with molecular oxygen in a secondary alcohol solvent (Oxidation-Reduction Hydration).6 During the course of our continuous studies on the catalytic enantioselective versions, we found out that the "Oxidative Kinetic Resolution" of secondary alcohols with the combined use of molecular oxygen and olefinic compounds was catalyzed by the optically active ketoiminatocobalt(II) complexes to afford the corresponding secondary alcohols of high optical purity. In the original "Oxidation-Reduction Hydration," the olefins were the substrate to be converted into the corresponding hydrated product whereas the secondary alcoholic solvent, such as 2-propanol, was employed as the reductant to be oxidized into the corresponding ketone. In the present "Oxidative Kinetic Resolution", the racemic secondary alcohol was the substrate for the cobalt-catalyzed aerobic oxidation reaction, while the olefinic compounds were employed as the oxygen acceptor to be converted into the corresponding ketone.

1. Jensen, D. R.; Pugsley, J. S.; Sigman, M. S. J. Am. Chem. Soc. 2001, 123, 7475-7476. Ferreira, E. M.; Stoltz, B. M. J.

Am. Chem. Soc. 2001, 123, 7725-7726. 2. Pawar, V. D.; Bettigeri, S.; Weng, S.-S.; Kao, J.-Q.; Chen, C.-T. J. Am. Chem. Soc. 2006, 128, 6308-6309. 3. Nakamura, Y.; Egami, H.; Matsumoto, K.; Uchida, T.; Katsuki, T. Tetrahedron 2007, 63, 6383-6387. 4. Arita, S.; Koike, T.; Kayaki, Y.; Ikariya, T. Angew. Chem. Int. Ed. 2008. 47, 2447-2449. 5. Kato, K.; Yamada, T.; Takai, T.; Inoki, S.; Isayama, S. Bull. Chem. Soc. Jpn. 1990, 63, 179-186.

Tohru Yamada, b 1958 in Hokkaido, Japan. The University of Tokyo (BS 1982, MS 1984, Ph.D. 1987, Prof. T. Mukaiyama). Mitsui Petrochemical Industries Ltd. (1987). Associate Prof. of Department of Chemistry, Keio University (1997), Professor (2002). Research field: asymmetric catalysis, aerobic oxidation, complex catalysts.

RR

OOxidativeKinetic

Resolution

H2O

R1 R2

OH

R1 R2

OH

R1 R2

OH

R1 R2

O

O2 cat.

N

O

N

OCo

O O

OO+(R) (S)

18

Organotellurium Mediated Living Radical Polymerization Initiated by Direct C-Te Bond Photolysis

Shigeru Yamago

Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan

[email protected]

Living radical polymerization (LRP) has become an

indispensable method for the synthesis of well defined

advanced polymeric materials. [1] LRP relies on

reversible generation of a reactive carbon-centered

radical from an inactive dormant species, and thermal

and chemical stimuli have been predominantly used

for the activation. [2] By contrast, LRP triggered by

photo stimuli has attracted great deal of attentions

because of potential application to photo-induced

fabrication of nano- architectures by, for example,

photolithography technique. The conditions would be

also suitable for production of biomaterials as the

polymerization can be conducted at ambient

temperature.

We report here the photo-induced

organotellurium-mediated LRP [3] by direct

photolysis of C-Te bond of the dormant species.

Highly efficient activation of dormant species

occurred by the irradiation of low intensity UV and

visible lights including sunlight, which was

ascertained by TEMPO trapping experiments.

Polyacrylates possessing various polar functional

groups with low to high molecular weight and low

polydispersity indices were synthesized. As far as we

know, this is the first example for the successful LRP

by direct photolysis of the dormant species.

[1] Macromolecular Engineering; Matyjaszewski, K.; Gnanou, Y.; Leibler, L., Eds.; Wiley-VCH: Weinheim,

2007.

[2] (a) Handbook of Radical Polymerization; Matyjaszewski, K.; Davis, T. P., Eds.; Wiley-Interscience: New York,

2002. (b) Moad, G.; Solomon, D. H. The Chemistry of Radical Polymerization; Elsevier: Amsterdam, 2006.

[3] Yamago, S. J. Polym. Sci., Part A: Polym. Chem. 2005, 44, 1-12.

Shigeru Yamago, b 1963 in Kochi, Japan. Tokyo Institute of Technology (BS 1986; MS

1988; Ph.D. 1991, Prof. E. Nakamura), Tokyo Institute of Technology (Assistant Prof. 1991,

Prof. E. Nakamura), Kyoto University (Assistant Prof. 1995, Associate Prof. 1997, Prof. J.

Yoshida), Osaka City University (Prof. 2003), Kyoto University (Prof. 2006). Research filed:

organic synthesis, polymer synthesis, radical chemistry, element chemistry.

19

Several Types of Intramolecular Double Cyclization from o,o'-Disubstituted Diphenylacetylenes

Shigehiro Yamaguchi

Department of Chemistry, Graduate School of Science, Nagoya University, Furo, Chikusa, Nagoya 464-8602,

Japan; [email protected]

One promising direction in the design of new

　-conjugated materials may be the construction of

fully ring-fused ladder frameworks. Their rigid and

coplanar structures, free from conformational disorder,

enhance the 　-conjugation and give rise to a set of

intriguing properties, such as intense luminescence,

high carrier mobility., and high thermal stability.

While various types of fascinating ladder molecules

have been synthesized in the last decade, a general

and versatile strategy to access such ladder skeletons

has still been highly demanded. We here report the

intramolecular double cyclization of o,o’-disubstituted

diphenylacetylenes as a new avenue to the ladder

materials. We have synthesized a series of ladder

molecules having not only the bridged stilbene

skeletons, but also more extended ladder

oligo(p-phenylenevinylene) skeletons, with various

main group elements (Si, P, B, S, Se) as the bridging

moieties [1]. Some recent results in this chemistry [2]

will be presented, together with the general ideas for

the design of the main group element-based

　-conjugated materials.

1. S. Yamaguchi, C. Xu, and T. Okamoto, Pure Appl. Chem., 78, 721-730 (2006).

2. A. Fukazawa, M. Hara, T. Okamoto. E.-C. Son, C. Xu, K. Tamao, and S. Yamaguchi, Org. Lett., 10, 913-916

(2008). H. Zhang, A. Wakamiya, and S. Yamaguchi, Org. Lett., 10, 3591-3594 (2008).

Shigehiro Yamaguchi, b 1969 in Mie, Japan. Kyoto Univ. (B. Eng., 1991); Kyoto Univ. (M. Eng., 1993, Prof. Y. Ito); Kyoto Univ. (Dr. Eng., 1997, Prof. K. Tamao), Assistant Prof. (1993, Kyoto Univ.), Associate Prof. (2003, Nagoya Univ.), Professor (2005–, Nagoya Univ.). Research fields: main group chemistry, structural organic chemistry, new synthetic methodologie

E'

E'

E

E

do uble cyclizat io n

E = SiR2, CR2, BR, PR, S, Se etc.

20

Symmetry Breaking in Centrosymmetric Cyclophandienes

Hsin-Chieh Lin,† Jui-Hung Hsu,‡ Chao-Kuei Lee,§

Oliver Yung-Hui Tai,‡ Chin-Hsien Wang,‡ Chih-Ming Chou,† Yi-Lin Wu,† and Tien-Yau Luh† †Department of Chemistry, National Taiwan University, Taipei, Taiwan 106

‡Department of Materials Science and Engineering and §Institute of Electro-optics,

National Sun Yat-sen University, Kaohsiung, Taiwan 80424


Centrosymmetric furan-containing cyclophandienes 1 and 2 exhibited extraordinarily large Stokes shifts and second-order nonlinear optical β values. The β values were comparable to those of respective cyclophenes where strong

hyperpoarizable interactions between two twisted π-systems (oligoaryl and bridging double bond) might take place.1 Symmetry breaking due to he unique structural feature may account for this unusual behavior.

O

O

Bu

Bu

O

O

O

O

Bu

Bu

Bu

Bu

1 β = 208 X 10-30 esu 2 β = 530 x 10-30 esu

250 300 350 400 450 500 550 600 6500.0

0.2

0.4

0.6

0.8

1.0

I nor

m

λ / nm

1. Lin, H.-C.; Lin, W.-Y.; Bai, H.-T.; Chen, J.-H.; Jin B.-Y.; Luh, T.-Y. Angew. Chem. Int. Ed. 2007, 46, 897-900.

Tien-Yau Luh 陸天堯. National Taiwan University (BS, 1967), University of Chicago (Ph.D. 1974), University of Minnesota (Postdoctoral fellow, 1975). Professor at the Chinese University of Hong Kong (1988-), Director at the Institute of Chemistry at Academia Sinica (2001-2004), Distinguish Fellow at the National Taiwan University. Professor at NYU (1989-), Professor (1993-). Research interests: new synthetic methodology, bio-mimetic, molecules and system, synergies between organic and polymer chemistry

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