abstracts - thieme.de · abstracts ix 2010 p27 5.1.19.7 a-halo-, a-hydroxy,-a-alkoxy-, and...

VII

Abstracts

2010 p 15.1.1.8 Germanium Hydrides

A. C. Spivey and C.-C. Tseng

This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of germanium hydrides, their properties, and synthetic reac-tions. It focuses on the literature published in the period 2001–2009.

Bu3GeH, BEt3air, toluene, rt

(syn/anti) 65:13

O

BnO

BnO

OR1

OPhSe

H H

H H O

BnO

BnO

OR1

H H

H HO

(E/Z) 1:1

H

78%

Keywords: germanes · germanium compounds · hydrides · germyl hydride · germaniumhydride · radical reduction · hydrogermylation · germylation · tris(2-furyl)germane · crosscoupling · germyl cation

2010 p 115.1.15.2 Germanium Cyanides


This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of germanium cyanides, their properties, and synthetic reac-tions. It focuses on the literature published in the period 2001–2009.

TMSCN, py, 40 oC

75%

GeNC CN

TMS TMSGeCl Cl

TMS TMS

Keywords: germanes · germanium compounds · cyanides · cyanation · halides · silver ·germole

2010 Updated Section • 2010 Completely Revised Contributions • New New Contributions

Science of Synthesis Knowledge Updates 2010/1 © Georg Thieme Verlag KG

http://www.thieme.de

http://www.ima-server.de

VIII Science of Synthesis Abstracts

2010 p 155.1.16.6 Acylgermanes


This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of acylgermanes, their properties, and synthetic reactions. It fo-cuses on the literature published in the period 2001–2009.

R1

O GeH+

CO (1 atm)

2.5 mol% Pd2Cl2(η3-C3H5)2

10 mol% But

But

O P

3R1 O

Getoluene, rt

O

3

3

Keywords: germanes · germanium compounds · enol ethers · [2+2] cycloaddition · azeti-dines · BINAP · alkynes · carbonylation · furans · radicals · polymerization · amides

2010 p 215.1.18.4 a-Halo- and a-Alkoxyvinylgermanes


This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of a-halo- and a-alkoxyvinylgermanes, their properties, andsynthetic reactions. It focuses on the literature published in the period 2001–2009.

H2O2, NaOH, R4X, Pd(PPh3)4

THF, 40−45 oC

R1

R2

GeR33

F

R1

R2

R4

F

R4 = Ph, CH=CHPh, CH=CMe2; X = Br, I

Keywords: germanes · germanium compounds · substitution · hydrometalation · carbo-metalation · halogenation · alkynes · germatranes · desulfonylation · cross coupling · pal-ladium(0) · styrenes






IXAbstracts

2010 p 275.1.19.7 a-Halo-, a-Hydroxy,- a-Alkoxy-, and a-Aminoalkylgermanes


This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of a-halo-, a-hydroxy-, a-alkoxy-, and a-aminoalkylgermanes,their properties, and synthetic reactions. It focuses on the literature published in the peri-od 2001–2009.

CH2Cl2, 6 h

GeMe3R1

BHCl2• OO

R1BCl2

GeMe3

CH2Cl2

0 oC, 30 min

HO OH3

R1B

GeMe3

O

O

NaOH

H2O2 R1OH

GeMe3

Keywords: germanes · germanium compounds · [1,2] rearrangements · oxo-carbenium ·oxonium · substitution · hydroboration · boronic ester · [3+2] cycloaddition · germenes · si-lylation · borylation

2010 p 355.1.20.4 Alkynylgermanes


This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of alkynylgermanes, their properties, and synthetic reactions.It focuses on the literature published in the period 2001–2009.

+R1 R1 GeR23

GeR23

RuH(Cl)(CO)(PCy3)2 (1−2 mol%)

toluene, 110 °C, 24−48 h

Keywords: germanes · germanium compounds · alkynes · [3+2] cycloadditions · hydro-stannylation · hydroboration · cross coupling · palladium(0) · substitution · cross metathe-sis · elimination · Pauson–Khand reaction · cyclopentenones





X Science of Synthesis Abstracts

2010 p 415.1.22.6 Aryl- and Heteroarylgermanes


This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of aryl- and heteroarylgermanes, their properties, and synthet-ic reactions. It focuses on the literature published in the period 2001–2009.

hν, Cu(BF4)2

MeOH/MeCN

Pyrex tube

R1Ge

Ar1

FF

PdCl2(NCMe)2

(2-Tol)3P, Ar2Br

TBAF, CuI

DMF, 120 oCAr1 Ar2

GeAr1

R1

Keywords: germanes · germanium compounds · cross coupling · Stille reaction · Hiya-ma–Denmark reaction · substitution · Barbier conditions · transmetalation · cycloaddi-tion · solid-phase synthesis · traceless linkers

2010 p 495.1.23.6 Vinylgermanes


This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of vinylgermanes, their properties, and synthetic reactions. Itfocuses on the literature published in the period 2001–2009.

Ru(Cl)H(CO)(PCy3)2

toluene, 24 hGeR13 + R2

R2

R13Ge

GeR13

R2

+

Keywords: germanes · germanium compounds · vinylgermanes · alkenylgermanes · b-ef-fect · hyperconjugation · hydrogermylation · heterogermylation · metallogermylation ·cross coupling · germatranes






XIAbstracts

2010 p 595.1.24.4 Propargyl- and Allenylgermanes


This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of propargyl- and allenylgermanes, their properties, and syn-thetic reactions. It focuses on the literature published in the period 2001–2009.

Mg, THF, )))Br + Et3GeCl 90%

GeEt3 + • GeEt3

1:3

Keywords: germanes · germanium compounds · propargylgermanes · allenylgermanes ·transmetalation · Grignard reagents · [2+2] cycloaddition

2010 p 635.1.25.3 Benzylgermanes


This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of benzylgermanes, their properties, and synthetic reactions.It focuses on the literature published in the period 2001–2009.

Ar1

R1

X

R2R3R4GeY

Ar1

R1

M Ar1

R1

GeR2R3R4

X = Cl, Br; M = MgCl, MgBr, Li

Keywords: germanes · germanium compounds · benzylgermanes · cross coupling ·boscalid

2010 p 695.1.26.6 Allylgermanes


This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of allylgermanes, their properties, and synthetic reactions. Itfocuses on the literature published in the period 2001–2009.

SnCl4

−78 oC, 15 minR1

3Ge OBn

OBnCl3Sn

H

R2CHO

−78 oC, 45 min

R2 OBn

OH

+R2 OBn

OH

>56%; dr >72:28

Keywords: germanes · germanium compounds · alkenylgermanes · allylation · ger-mylene · p-allylpalladium(0) · metallogermanes · Baylis–Hillman · germyl radicals





XII Science of Synthesis Abstracts

2010 p 775.1.27.4 Alkylgermanes


This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of alkylgermanes, their properties, and synthetic reactions. Itfocuses on the literature published in the period 2001–2009.

AIBN

hν or BEt3air

S

Ge

S

H

But

TMS

TMS

CO2Me

S

Ge

S But

TMS

TMS

CO2Me

55%; >96% de

Keywords: germanes · germanium compounds · alkenylgermanes · ADMET · germylene ·hydrogermylation

2010 p 819.11.4 Selenophenes

J. Schatz and M. Seßler

This manuscript is intended to update the first report on the synthesis of selenophenes inScience of Synthesis and will briefly summarize essential, more recent findings concerningthis heterocyclic system in the first decade of the new millennium. During this time, ap-plications of selenophene-based materials in organic electronics and photonics receivedconsiderable interest, and selenophene-containing p-conjugated compounds have beenproposed as organic magnetic materials.

O

R1

SeO2

dioxane/pyridine (5:1)

80 °C

O

SeR1

Keywords: selenophenes · active methylene compounds · selanylenynes · cyclization ·aromatization · metal–halogen exchange






XIIIAbstracts

2010 p 999.12.3 Tellurophenes

J. Schatz and M. Seßler

This manuscript is intended to update the earlier report on the synthesis of tellurophenesin Science of Synthesis, and summarizes essential, more recent findings concerning thisheterocyclic system in the first decade of the new millennium. The decade 2000–2010saw an increasing interest in organic molecules as functional materials, shifting the focusaway from biological or pharmaceutical application. This trend could especially be ob-served for thiophenes, leading, not surprisingly, also to an increasing pursuit of potentialapplications of tellurophenes.

R1

BuTe

R2

1. BuTeBr3, MeCN, rt

2. NaBH4, EtOH, rt, 1 h

TeR1 R2

TeBu

Keywords: tellurophenes · tellanylenynes · cyclization · aryl cross coupling

2010 p 10911.9.5 Isoxazoles

P. Margaretha

This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of isoxazoles (1,2-oxazoles). It focuses on the literature publish-ed in the period 2001–2009.

Cl NOH

Br O

9

+CuI

84%

ON

O

Br

9

Keywords: isoxazoles · isoxazol-5-ones · dipolar cycloadditions · oximes · nitrile oxides ·cyclization · multicomponent coupling · regioselectivity





XIV Science of Synthesis Abstracts

2010 p 13311.10.5 1,2-Benzisoxazoles and Related Compounds

S. H�rtinger

This update deals with important general methods for the synthesis of 1,2-benzisoxazolederivatives that have not been discussed in the original Section 11.10 or in Houben–Weyl,Vol. E 8a. Literature published until 2009 is reviewed.

OHR2

N

O

R1

R2O

NR1

O

OH

Ph3P, DEAD, THF

0−25 oC, 30 min

R1 = alkyl, cycloalkyl, aryl; R2 = alkyl, alkoxy, nitro, acylamino, acyloxy

78−92%

Keywords: 1,2-benzisoxazoles · cyclization · ring closure · coupling reactions · aromatiza-tion

2010 p 15311.13 Product Class 13: Benzoxazoles and Other Annulated Oxazoles

M. Schn�rch, J. H�mmerle, and P. Stanetty

This manuscript is a revision of the earlier Science of Synthesis contribution describingmethods for the synthesis of benzoxazoles (benzo[d]oxazoles, 1,3-benzoxazoles) and relat-ed compounds such as benzoxazol-2-ones and other heteroannulated derivatives. Classi-cal routes to benzoxazoles involve the intermolecular cyclization of 2-aminophenols orintramolecular cyclization of N-phenylcarboxamides, but more recent developmentswith different approaches are included as well.

OH

NH2 N

O

Deoxo-Fluor, iPr2NEt

K2CO3, 0 oC, 2 h

CO2H7

7

7797%

Keywords: benzoxazoles · benzoxazol-2-ones · 2-aminophenols · N-phenylcarboxamides ·cyclization · annulation · Beckmann rearrangement






XVAbstracts

2010 p 20711.15.4 Isothiazoles

M. Sainsbury

This manuscript is an update to the earlier Science of Synthesis contribution describing thesyntheses of isothiazoles and, in particular, advances in classical methods. Applicationsof well-known coupling methods to isothiazoles are also illustrated. The coverage focuseson the literature published in the period 2001–2009.

O SNPh Ph

Ph

Ph

O

H2NCO2Et, SOCl2, py, benzene, reflux

98%

Keywords: isothiazoles · isothiazol-3(2H)-ones · dipolar cycloadditions · nitrile sulfides ·macrocycles · cyclization · coupling reactions · rearrangements

2010 p 24911.16.3 Benzisothiazoles

M. Sainsbury

This manuscript is an update of the earlier Science of Synthesis contribution describingmethods for the syntheses of 1,2-benzisothiazoles (benzo[d]isothiazoles) and related com-pounds such as 2,1-benzisothiazoles (benzo[c]isothiazoles) and other heteroannulated de-rivatives, including 2-arylisothiazolo[5,4-b]pyridin-3(2H)-ones. New routes to 1,2-benziso-thiazoles involve the intermolecular cyclizations of benzyne (generated in situ) with ni-triles sulfides. Developments in approaches to 1,2-benzisothiazol-3(2H)ones are also de-scribed.

IPh

TMS

TBAF

SN

NEt2

N

Et

Et

N S+93%

OTf−

Keywords: 1,2-benzisothiazoles · 2,1-benzisothiazoles · saccharin · 1,3-dipolar addition ·cyclization · cycloaddition · annulation · Suzuki coupling

2010 p 26711.17.6 Thiazoles

P. A. Koutentis and H. A. Ioannidou

This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of aromatic thiazoles and the tautomers of heterosubstitutedthiazoles. It focuses on the literature published in the period 1999–2009.

N

Sthiazole

NH

S3H-thiazole

X

N

S5H-thiazole

N

S4H-thiazole

X

X

Keywords: thiazoles · ring closure · aromatization · ring transformation · substituentmodification





XVI Science of Synthesis Abstracts

2010 p 39311.18.5 Benzothiazoles

H. Ulrich

This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of benzothiazoles. Recent interest in this area has in partbeen generated by the discovery that some 2-(aminophenyl)benzothiazoles, in particular,possess potent anticancer and other biological activities.

HN

S

NPh

Ph

S

R2

R3

PhI(OCOCF3)2, CF3CH2OH

25 oC, 30 minR2

R3

R1 R1

Keywords: benzothiazoles · 2-aminobenzenethiols · N-phenylthioamides · oxidative cy-clization · solid-phase synthesis

2010 p 40511.20.3 Isoselenazoles

K. Shimada

This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of isoselenazoles. It focuses on the literature published in theperiod 2002–2009.

1. KSeCN

2. NH4ClCHO

Cl

R1

R2

R1

R2

SeN

Keywords: isoselenazoles · 4,5-diarylisoselenazoles · 3-(trihalomethyl)isoselenazoles ·isoselenazole-3-carboxylic acids · 3,5-disubstituted isoselenazoles · bis(N,N-dimethylcarba-moyl) diselenide · ring closure · cyclization · substituent modification






XVIIAbstracts

2010 p 41311.21.5 Annulated Isoselenazole Compounds

K. Shimada

This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of annulated isoselenazole compounds. It focuses on the litera-ture published in the period 2002–2009.

SeN Pri

O

air

NHPri

O

NHPri

1. BuLi, TMEDA, THF

2. Se

NHPri

NHPri

O

NHPri

SeH

O O

O

Keywords: 1,2-benzisoselenazoles · 1,2-benzisoselenazol-3(2H)-ones · N,N¢-dialkylisoph-thalamides · ring closure · ortho-metalation · selenation · oxidation

2010 p 41711.22.4 Selenazoles

K. Shimada

This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of selenazoles. The synthesis of selenazoles by ring construc-tion using selenocarbonyl compounds, such as selenoamides and selenoureas, is report-ed.

Se

NH2R1Se

N

O

R2Br

R3

R3

R2

R1

Keywords: selenazoles · ring closure · substituent modification · side-chain modification ·dithioimidocarbonates · selenoamides · selenoureas · a-halo ketones · a-halo acetoni-triles · selenazadienes · benzylic oxidation





XVIII Science of Synthesis Abstracts

2010 p 45511.23.3 Annulated Selenazole Compounds

K. Shimada

This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of annulated selenazole compounds. It focuses on the litera-ture published in the period 2002–2009.

CuI, DBU, THF, rtNC

X

+ Se +Se

NNuNuH

Keywords: benzoselenazoles · 2-halophenyl isocyanides · annulation · ring closure · sub-strate modification · [1,3]selenazolo[4,5-d]triazines · selenazole-5-carbonitriles · benzose-lenazol-3-ium salts · benzoselenazole-1,7-diones · squarylium dyes · azo dyes

2010 p 46711.25.4 Isotellurazoles, and Annulated Isotellurazole and Tellurazole Compounds

K. Shimada

This manuscript is an update to the earlier Science of Synthesis contribution describingmethods for the synthesis of isotellurazoles, and annulated isotellurazole and tellurazolecompounds. It focuses on the literature published in the period 2002–2009. An efficient,one-pot procedure for the preparation of 3,5-disubstituted isotellurazoles from alkynonesand bis(N,N-dimethylcarbamoyl) ditelluride is reported.

TeN

R2

R1

TeN

R2

R1

R1

R2

OMe2N Te

O

Te NMe2

O

NaBH4

Me2N Te

O R1

H2NOSO3H

MeOH, reflux

O

Ph3P, CHCl3

heat

O R2

Keywords: isotellurazoles · isotellurazole Te-oxides · benzotellurazoles · cyclization · ringclosure · deoxygenation · ortho-metalation · telluration · oxidation






XIXAbstracts

2010 p 47316.20.3 Pyridopyrazines

J. Zhang

This manuscript is an update of the original Science of Synthesis chapter and includes meth-ods for the preparation of pyrido[2,3-b]pyrazines and pyrido[3,4-b]pyrazines described inthe literature up to 2010. Methods proceeding via condensation of pyridinediamineswith carbonyl compounds and the application of halopyrido[2,3-b]pyrazines in palladi-um-catalyzed cross-coupling reactions are covered.

N

NH2

NH2 N

N

N

O

O Ph

+

10 mol% Bi(OTf)3

H2O, rt, 5 minPh

H92%

Keywords: pyridopyrazines · ring closure · condensation reactions · dicarbonyl com-pounds · cross-coupling reactions · pyridinediamines

2010 p 48731.4.2.2 Iodoarenes

S. R. Waldvogel

This manuscript is an update of the 2007 Science of Synthesis contribution describing meth-ods for the synthesis of iodoarenes published in the period 2006–2010.

X

R1

I

R1

X = H, Br

Keywords: iodination · iodine · iodo compounds · phenols · napthoquinones · benzoqui-nones · halodecarboxylation · fluorine compounds · electrophilic aromatic substitution ·aryl compounds · halogenation · activation of C–-H bonds · acid halides





abstracts - thieme.de · abstracts ix 2010 p27 5.1.19.7 a-halo-, a-hydroxy,-a-alkoxy-, and...

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