N-Heterocyclic Carbene-Mediated Enantioselective Addition of Phenols to Unsymmetrical Alkylarylketenes

被引：72

作者：

Concellon, Carmen ^{[1
]}

Duguet, Nicolas ^{[1
]}

Smith, Andrew D. ^{[1
]}

机构：

[1] Univ St Andrews, Sch Chem, EaStCHEM, St Andrews KY16 9ST, Fife, Scotland

来源：

ADVANCED SYNTHESIS & CATALYSIS | 2009年 / 351卷 / 17期

基金：

英国工程与自然科学研究理事会;

关键词：

asymmetric catalysis; enantioselectivity; esters; ketenes; N-heterocyclic carbenes; organocatalysis; INTERMOLECULAR STETTER REACTION; DIELS-ALDER REACTIONS; CATALYZED RING EXPANSION; SYNTHESEN MIT KETENEN; C-CARBOXYL TRANSFER; ASYMMETRIC-SYNTHESIS; ALPHA; BETA-UNSATURATED ALDEHYDES; SECONDARY ALCOHOLS; ZWITTERIONIC POLYMERIZATION; STEREOSELECTIVE-SYNTHESIS;

D O I：

10.1002/adsc.200900538

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

Chiral N-heterocyclic carbenes (NHCs) mediate the enantioselective addition of 2-phenylphenol to unsymmetrical alkylarylketenes, delivering alpha-alkyl-alpha-arylacetic acid derivatives with good levels of enantiocontrol (up to 84% ee). Enantiodivergent stereochemical outcomes are observed using 2-phenylphenol and benzhydrol in the NHC-promoted esterification reaction using a triazolium precatalyst derived from pyroglutamic acid, consistent with distinct mechanistic pathways operating within these processes.

引用

页码：3001 / 3009

页数：9

共 122 条

[1] Synthesis of a new insoluble polymer-supported chiral alcohol auxiliary and its first application to nucleophilic addition to ketenes [J].

Akkari, R ;

Calmes, M ;

Mai, N ;

Rolland, M ;

Martinez, J .

JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (17) :5859-5865

[2] Direct organocatalytic synthesis of enantiopure succinimides from β-lactam aldehydes through ring expansion promoted by azolium salt precatalysts [J].

Alcaide, Benito ;

Almendros, Pedro ;

Cabrero, Gema ;

Ruiz, M. Pilar .

CHEMICAL COMMUNICATIONS, 2007, (45) :4788-4790

[3] STEREOSELECTIVE ACYLATION OF RACEMIC SECONDARY ALCOHOLS WITH PHENYLTRIFLUOROMETHYLKETENE AS AN EXPERIMENTAL TEST OF STEREOCHEMICAL ANALOGY MODEL [J].

ANDERS, E ;

RUCH, E ;

UGI, I .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1973, 12 (01) :25-29

[4]

[Anonymous], ANGEW CHEM

[5]

[Anonymous], 2005, ANGEW CHEM

[6]

[Anonymous], 2004, ANGEW CHEM

[7] The highly enantioselective transformation of silylketenes into α-silylthioesters catalysed by cinchona alkaloids [J].

Blake, AJ ;

Friend, CL ;

Outram, RJ ;

Simpkins, NS ;

Whitehead, AJ .

TETRAHEDRON LETTERS, 2001, 42 (15) :2877-2881

[8] N-heterocyclic carbene-catalyzed redox amidations of α-functionalized aldehydes with amines [J].

Bode, Jeffrey W. ;

Sohn, Stephanie S. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (45) :13798-+

[9] SOFT DRUGS - A NEW CLASS OF ANTICHOLINERGIC AGENTS [J].

BODOR, N ;

WOODS, R ;

RAPER, C ;

KEARNEY, P ;

KAMINSKI, JJ .

JOURNAL OF MEDICINAL CHEMISTRY, 1980, 23 (05) :474-480

[10] HALOGENATED KETENES .8. DIHALOKETENE REACTIVITIES IN AN ACYLATION REACTION [J].

BRADY, WT ;

VAUGHN, WL ;

HOFF, EF .

JOURNAL OF ORGANIC CHEMISTRY, 1969, 34 (04) :843-&

← 1 2 3 4 5 6 7 8 9 10 →