graphical contents list

Tetrahedron Letters Vol. 55, Issue 6, 2014

Contents

DIGEST PAPER

Transition-metal-catalyzed ketone-directed ortho-C–H functionalization reactions pp 1121–1126

Qing-Zhong Zheng, Ning Jiao*

R

O

M: Ru, Rh, Pd, or Ir

H C-H functionalizationR

O

FG

In the past 20 years, organic chemists have made significant contributions to the development of transition-metal-catalyzed ketone-directed ortho-C–H functionalization. Theseinclude Ru, Rh, Pd and Ir-catalyzed ketone-directed C–C and C-heteroatom (O, N, Cl, Br, I) bond forming reactions. This article summarizes the developments of Ru, Rh, Pd andIr-catalyzed ketone-directed ortho-C–H functionalization reactions in the past two decades.

COMMUNICATIONS

LL-Proline catalyzed efficient and convenient synthesis of substituted 2H-chromenes by three-component reaction pp 1127–1131

L. Chandrasekhara Rao, H. M. Meshram*, N. Satish Kumar, N. Nageswara Rao, N. Jagadeesh Babu

O

O

OR

O O

R-OHL-Proline,

RT, 6-8 h

CHO

OHR1

R2

R1

R2

+

R = methyl, ethyl, n-butyl, n-octyl, propargyl,p -methoxy benzylR1 = H, OCH3, R2 = H, Cl, Br, NO2

The trans opening of ethylene diamine tetra acetic acid bis anhydride (EDTAA) with cystine-di-OMe: one-stepsynthesis of bihelical systems

pp 1132–1135

Santhosh Reddy Naini, Subramania Ranganathan*, Jhillu Singh Yadav*, A. V. S. Sarma*, K. V. S. Ramakrishna*,Ramakrishnan Nagaraj*, J. Richard Premkumar, G. Narahari Sastry*

N

N

COOMe

MeOOC

O

SS

NH

(R)

COOMe

(R)MeOOC

HN

O 4

COOMe

MeOOC

MeOOC

COOMeN

N

SS

HN

(S)

(S)

NH

CH3H3C

CH3

H3C

9

O

O

1111

Contents lists available at ScienceDirect

Tetrahedron Letters

journal homepage: www.elsevier .com/ locate/ tet le t

Keggin-type Bronsted dodecatungstophosphoric acid: a quasi homogenous and reusable catalyst system for liquidphase Beckmann rearrangement

pp 1136–1140

Gagandeep Kaur, Jaspreet Kaur Rajput*, Priya Arora, Nisha DeviEfficient

Clean

SimpleRecyclable

GreenC NOH

nC NOH

R

R'

n = 0, X = S, R" = CH3

n = 1, X = N, R" = CH2CH3

n = 0, 1

NH

OnC N

R'

OR

H

X

nC

R''

NOHX

n

HN

R''

O

R=C6H5, R’=C6H5

R=4- Cl-C6H4, R’=C6H5

R=C6H5, R’=CH3

R=4-Cl-C6H4, R’= CH3

R=2-OH-C6H4, R’= CH3

R=4-OCH3-C6H4, R’= CH3

R=4-CH3-C6H4, R’= CH3

R=4-NO2-C6H4, R’= CH3

H3PW12O40

Refluxing, CH3CN

0.05mmol

Beckmann rearrangement of ketoximes to N-substituted amides and lactams using dodecatungstophosphoric acid (DTPA).

Pd(II)-catalyzed deprotection of acetals and ketals containing acid sensitive functional groups pp 1141–1144

Francisco Juliá-Hernández, Aurelia Arcas, José Vicente*

Stereoselective synthesis of the right-hand segment of tubiferal A pp 1145–1147

Takahiro Hiramatsu, Motomasa Takahashi, Keiji Tanino*

Tubiferal A

CN

AcO OMOMO

OMe

OMe

MOMO

O

O

H

HH

O

O

HO

HO

H

H

HO H

H

H

A practical and efficient synthesis of 6-carboalkoxy-13-cycloalkyl-5H-indolo[2,1-a][2]benzazepine-10-carboxylic acidderivatives

pp 1148–1153

Piyasena Hewawasam*, Yong Tu, Thomas W. Hudyma, Xiaofan Zhang, Robert G. Gentles, John F. Kadow, Nicholas A. Meanwell

MeO

OP(OMe)2

O

11 6a

NMeO2C

CO2Me

Cs2CO3, DMF60 °C, 3h; 96%

HN

CHOMeO2C

12

1112 Contents / Tetrahedron Letters 55 (2014) 1111–1119

Synthesis of 4-aryl-6-indolylpyridine-3-carbonitriles and evaluation of their antiproliferative activity pp 1154–1158

Naglaa Salem El-Sayed, Amir Nasrolahi Shirazi, Magda Goda El-Meligy, Ahmed Kamel El-Ziaty, David Rowley, Jiadong Sun,Zenat Adeeb Nagib*, Keykavous Parang*

NH

ArCN

O

NH 13a-e

N

ArCN

X

NHX = -Cl 14a-e

X = -NH(CH)2NH2 15a-e

Synthesis of imidazo[1,2-a]pyridine in the presence of iodine–water catalytic system pp 1159–1163

I. R. Siddiqui*, Pragati Rai, Rahila, Anushree Srivastava, Shayna Shamim

N

NH2 CHON

NI2 (10mol%)

water /600C6.0-6.5h65-87%

R1R2 R3

R1R2

1(a-d) 2(a-h) 3(a-b)5(a-m)R3

Studies directed toward the synthesis of caylobolide A: convergent synthesis of C21–C40 subunit pp 1164–1167

J. S. Yadav*, N. Swapnil, M. Venkatesh, A. R. Prasad

O

OOHOHOH

HO

HO

OH OH OH OH

OTBS

OTBS

OHOHOBn

BnO

Caylobolide A

An efficient and regioselective one-pot multi-component synthesis of pyrimido[4,5-d]pyrimidine derivatives in water pp 1168–1170

Swarup Majumder*, Pallabi Borah, Pulak J. Bhuyan*

NCS

X

ArCHO N

N

H2N

O

OR

+ + N

NH

N

N

O

OR

Ar

S

X

p-TSA

Water,Reflux

1-2h1 2 3 4

X=H, CH3 R=H, CH3

Contents / Tetrahedron Letters 55 (2014) 1111–1119 1113

Reaction-based colorimetric and fluorogenic signaling of hydrogen sulfide using a 7-nitro-2,1,3-benzoxadiazole–coumarin conjugate

pp 1171–1174

Jihee Bae, Jiyoung Choi, Tae Jung Park, Suk-Kyu Chang*

First total synthesis of prunustatin A pp 1175–1177

Shuhei Yamakoshi, Eiji Kawanishi*

O

O OO

O O

BocHN

O

HOCO2H

Ph

Prunustatin A

OHCPh

OBnOtBuO2C

OBr

HO

CO2SEMBocHN BnO

CO2H

Macrocyclization (C5-O4 bond)

Reformatsky reaction

O

O OO

O

O

O

Ph

O

OHN

O

OHNHCHO

4

5

Synthesis of 1,6-dihydropyrimidines via copper-catalyzed multistep cascade reactions between O-propargylicaldoximes and isocyanates

pp 1178–1182

Itaru Nakamura*, Toshiki Onuma, Dong Zhang, Masahiro Terada

N NO

R2

R1

N

R3

O • NTs

+

R3

Ts

R2 R1

cat. CuBr / SPhos

− CO2

H

H

An expedient synthesis of 3-alkylideneoxindoles by Ti(OiPr)4/pyridine-mediated Knoevenagel condensation pp 1183–1187

Hyun Ju Lee, Jin Woo Lim, Jin Yu, Jae Nyoung Kim*

NO

H

Ph

O

Ti(OiPr)4 Me

NOTi(OiPr)3

H

H

NO

H

Me Ph

NO

H

Ph Me

+

Z (78%) E (15%)

pyridine

H H


Aerobic oxidative desymmetrization of meso-diols with bifunctional amidoiridium catalysts bearing chiralN-sulfonyldiamine ligands

pp 1188–1191

Junki Moritani, Yasuharu Hasegawa, Yoshihito Kayaki, Takao Ikariya*

cat

NIr

N

H

C6H5

C6H5

Mscatair, 1 atmTHF30 °C

+ 1/2 O2 + H2O

O

OH

OH

OH

n n

S/C = 10[diol] = 0.1 Mn = 1–3

up to 99% yieldup to 99% ee

Synthesis of 1-acetyl-2-silyoxycycloheptane derivatives via highly stereoselective formal [5+2] cycloaddition reaction pp 1192–1195

Mami Kudo, Fumikatsu Kondo, Hideki Maekawa, Tadashi Shimizu, Masaaki Miyashita, Keiji Tanino*

Thionium ion promoted Michael acceptor: a sequence of Pummerer/Michael reactions for the stereoselective synthesisof 5-(1-(arylthio)vinyl)-oxazolines

pp 1196–1198

Shimin Xu, Qianyun Zhang, Hongwei Zhou*

HN

SAr

O

R2

CF3

O

R1

OHN

SAr

O

R2 S

ON

R1

R2R1

O

ArDCM, -20 oC

TFAA

up to 85% yield

Pd/C: an efficient and heterogeneous protocol for oxidative carbonylation of diols to cyclic carbonate pp 1199–1202

Sujit P. Chavan, Bhalchandra M. Bhanage*

+HO OH

CO

R1

OO

R2

O

R2R1

R1, R2 = -H, -Alkyl, -Ph-CH2Cl, -CH2OAr

KI, NaOAc

Pd/C

O2, DME3-8 h

The present protocol involves highly efficient and practical approach for the synthesis of cyclic carbonates via oxidative carbonylation of diols, glycerol andits derivatives using Pd/C as heterogeneous and recyclable catalyst.


Synthesis of 9-oxiranyl-9H-purine derivatives in b-cyclodextrin cavity pp 1203–1206

Qian Zhang*, Yong-Zhen Huang, Jun-Hui Yang, Bai-Wei Ma, Gui-Rong Qu, Hai-Ming Guo*

N

NN

NR1

Oxone

R2

R

N

NN

NR1

R2

R O

β -CD, OO

OHHO

OH

β -CD

H2O, RT

Synthesis of benzofuran-containing spirolactones from diarylcyclopropenones pp 1207–1211

Jia-Ru Syu, Chi-Hui Lin, Chiao-Wen Kuo, Ding-Yah Yang*

OOMeOMe

MeO O

O Ph

PhPh Ph

O

MeO

O

O

O

O Ph

Ph

cat. CuBr

An efficient route for the construction of a novel benzofuran-containing spirolactone skeleton via copper-catalyzed heterodimerization of1,2-diarylcyclopropenones followed by sequential demethylations of highly strained cyclopropene-derived spirolactones is reported.

One-pot synthesis of aryl alkyl thioethers and diaryl disulfides using carbon disulfide as a sulfur surrogate in thepresence of diethylamine catalyzed by copper(I) iodide in polyethylene glycol (PEG200)

pp 1212–1217

Habib Firouzabadi*, Nasser Iranpoor*, Arash Samadi

Na

Et2N

SS

(ii) ArZ, CuI (10 mol%) PEG200, 110 -130 °C

(iii) KOH, H2OEt2NH + CS2

ArSSAr

r.t.

(i) NaOH(aq)

ArSRRBr

HCl (conc)

( 30 examples)

( 6 examples)

Z = I, OTs, Br, Ar = phenyl, 4-methylphenyl, 4-methoxyphenyl, naphthalen-1-yl, 4-trifluoromethylphenyl, 3,4-dichlorophenyl, R = benzyl, n-butyl, cyclohexyl.

Elongation of the molecular probe DDNP with phenylethynylidene or phenyldiazenylidene spacers pp 1218–1221

Luka Rejc, Jan Fabris, Armin Adrovic, Marta Kasunic, Andrej Petric*

N

NN

NN

N

NN

N

NN

DDNP 105


Synthesis of tris(b,b,c-oximinoalkyl)amines from aliphatic nitro compounds and methyl vinyl ketone pp 1222–1225

Elena A. Shalamova, Yeosan Lee, Garam Chung, Artem N. Semakin*, Jinho Oh, Alexey Yu. Sukhorukov*, Dmitry E. Arkhipov,Sema L. Ioffe, Sergey E. Semenov

N(OTMS)2

R3

N

R2N

OH

R3

N OHR1

NR4O

N(OTMS)2

R2O

R1

R4O NH2

[NH3]

A green and convenient protocol for the synthesis of novel pyrazolopyranopyrimidines via a one-pot, four-componentreaction in water

pp 1226–1228

Majid M. Heravi*, Farnoush Mousavizadeh, Nazanin Ghobadi, Mahgol Tajbakhsh

Chemoselective aminomethylation of bifunctional substrates: carbonyl versus phenolic hydroxyl, carbonyl versuspyrazole and pyrrole versus phenolic hydroxyl as competing activating groups

pp 1229–1233

Gheorghe Roman*

OH

CH3

O

or

Ar

O

NN

CH3

CH3

NHO

H3C

H3C

Formation of dilithiated bis-(1H-pyrazol-1-yl)alkanes and their application in the synthesis of diboronic acids pp 1234–1238

Krzysztof Durka, Agnieszka Górska, Tomasz Klis*, Janusz Serwatowski, Krzysztof Wozniak

N N

N N

(CH2)

1. t-BuLi, -78 °C, THF2. B(OEt)3

3. H3O+

n

Br

Br

N N

N N

(CH2)n

Br

Br

X

X

X = CONHt-Bun = 1,2,3,8

1. LDA, -78 °C, THF2. t-BuNCO3. H3O+

N N

N N

(CH2)n

B(OH)2

B(OH)2

X

X

X = CONHt-Bu


Azo-coupling of pyrazole-3(5)-diazonium chlorides with cyanothioacetamide: a convenient synthesis ofpyrazolo[5,1-c][1,2,4]triazine-3-carbothioamides

pp 1239–1242

Irina V. Ledenyova*, Vitaly V. Didenko, Victor V. Dotsenko, Khidmet S. Shikhaliev

N

R Ar

HN N N

Cl

H2NNS

N

R Ar

N NN

H2NNH2S

Hantzsch-typeproducts

Oxidationproducts

Synthesis of chiral butenolides using amino-thiocarbamate-catalyzed asymmetric bromolactonization pp 1243–1246

Chong Kiat Tan, Jun Cheng Er, Ying-Yeung Yeung*

R2

R1

O

OHR2R1

OO

1. NBSCHCl3/hexane (1:1), -78 oC2. Et3N, 5 min

N

HN

O

S

NH

(10 mol%)

up to 99% yield58% ee

Synthesis of phosphorus containing medium ring heterocycles by sequential Claisen rearrangement and ring closingmetathesis

pp 1247–1250

K. C. Majumdar*, Raj Kumar Nandi, Sintu Ganai

O PO OEt

n = 0, 1n RCM Protocol

Aromaticor

Heterocycles

Aromaticor

Heterocycles

POO OEt

n

14 examples(65-92%) Phosphorus heterocycles

OHAromaticor

Heterocycles

A one-pot multicomponent synthesis of polysubstituted thiophenes via the reactions of an isocyanide, a-haloketones,and b-ketodithioesters in water

pp 1251–1254

Firouz Matloubi Moghaddam*, Mohammad Reza Khodabakhshi, Arash Latifkar

SMeS

O

R

O

Ar

O S

SMe

NC ,

RO Br

2)

1)

H2O, 6 h

, K2CO3, 6 h

Ar


Synthesis of an azabicyclic framework towards (±)-actinophyllic acid pp 1255–1257

Danny Mortimer, Matthew Whiting, Joseph P. A. Harrity*, Simon Jones*, Iain Coldham*

NH

OTBS

NBoc

CO2Me

CO2MeCHO

BPh3 / H2Otrifluorotoluene

CO2MeCO2Me

HN

HH

O

NBoc

A ‘turn-on’ fluorescent chemosensor based on rhodamine-N-(3-aminopropyl)-imidazole for detection of Al3+ ions pp 1258–1262

Zhengqiang Li, Qiuping Hu, Chunxiao Li, Jintao Dou, Jiaojie Cao, Weikai Chen, Qingzeng Zhu*

*Corresponding authorSupplementary data available via ScienceDirect

Abstracted/indexed in: AGRICOLA, Beilstein, BIOSIS Previews, CAB Abstracts, Chemical Abstracts, Chemical Engineering andBiotechnology Abstracts, Current Biotechnology Abstracts, Current Contents: Life Sciences, Current Contents: Physical,Chemical and Earth Sciences, Current Contents Search, Derwent Drug File, Ei Compendex, EMBASE/Excerpta Medica, Medline,PASCAL, Research Alert, Science Citation Index, SciSearch. Also covered in the abstract and citation database Scopus�. Full textavailable on ScienceDirect�

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