The Mechanism and an Improved Asymmetric Allylboration of Ketones Catalyzed by Chiral Biphenols

被引：139

作者：

Barnett, David S. ^{[1
]}

Moquist, Philip N. ^{[1
]}

Schaus, Scott E. ^{[1
]}

机构：

[1] Boston Univ, Ctr Chem Methodol & Lib Dev, Dept Chem, Boston, MA 02215 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2009年 / 48卷 / 46期

关键词：

boron; homogeneous catalysis; reaction mechanisms; synthetic methods; CARBONYL-ENE REACTION; BRONSTED ACID; ENANTIOSELECTIVE ALLYLATION; SOLVENT-FREE; LEWIS-ACID; INDIUM(III) COMPLEX; EFFICIENT CATALYSTS; KINETIC RESOLUTION; TERMINAL EPOXIDES; MANNICH REACTION;

D O I：

10.1002/anie.200904715

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Giving it a boost: A mechanistic study of the enantioselective asymmetric titled reaction with allyldiisopropoxyborane catalyzed by chiral biphenols revealed a key ligand exchange process which liberates isopropyl alcohol. The addition of iPrOH to the reaction increases the overall rate and enantioselectivity. As a result an improved reaction, employing allyldioxaborinane with 1 and tBuOH, resulted in high product yields and enantioselectivities.© 2009 Wiley-VCH Verlag GmbH &. Co. KCaA.

引用

页码：8679 / 8682

页数：4

共 58 条

[1]

[Anonymous], ANGEW CHEM

[2] ORGANOBORANES .53. A HIGH-FIELD VARIABLE-TEMPERATURE H-1 AND B-11 NMR-STUDY OF THE EFFECTS OF SOLVENT AND STRUCTURE ON REACTIVITY IN ALLYLBORATION [J].

BROWN, HC ;

RACHERLA, US ;

PELLECHIA, PJ .

JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (06) :1868-1874

[3] BINOL-Ti-catalyzed synthesis of tertiary homoallylic alcohols: The first catalytic asymmetric allylation of ketones [J].

Casolari, S ;

D'Addario, D ;

Tagliavini, E .

ORGANIC LETTERS, 1999, 1 (07) :1061-1063

[4]

Chemler S.R., 2000, MODERN CARBONYL CHEM, P403

[5] A Bronsted acid catalyst for the enantioselective protonation reaction [J].

Cheon, Cheol Hong ;

Yamamoto, Hisashi .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (29) :9246-+

[6] On the use of mixtures of organotin species for catalytic enantioselective ketone allylation - a detective story [J].

Cunningham, A ;

Mokal-Parekh, V ;

Wilson, C ;

Woodward, S .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2004, 2 (05) :741-748

[7]

Cunningham A., 2002, SYNLETT, P43

[8]

Denmark S.E., 2000, MODERN CARBONYL CHEM, P299

[9] Efficient catalytic enantioselective synthesis of unsaturated amines: Preparation of small- and medium-ring cyclic amines through Mo-catalyzed asymmetric ring-closing metathesis in the absence of solvent [J].

Dolman, SJ ;

Sattely, ES ;

Hoveyda, AH ;

Schrock, RR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (24) :6991-6997

[10] Chiral Bronsted acid-catalyzed direct asymmetric Mannich reaction [J].

Guo, Qi-Xiang ;

Liu, Hua ;

Guo, Chang ;

Luo, Shi-Wei ;

Gu, Yi ;

Gong, Liu-Zhu .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (13) :3790-+

← 1 2 3 4 5 6 →