Hydroxymethylation beyond Carbonylation: Enantioselective Iridium-Catalyzed Reductive Coupling of Formaldehyde with Allylic Acetates via Enantiotopic π-Facial Discrimination

被引：47

作者：

Garza, Victoria J. ^{[1
]}

Krische, Michael J. ^{[1
]}

机构：

[1] Univ Texas Austin, Dept Chem, Austin, TX 78712 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2016年 / 138卷 / 11期

关键词：

ALDEHYDE OXIDATION LEVEL; ASYMMETRIC ALPHA-HYDROXYMETHYLATION; C BOND FORMATION; AQUEOUS FORMALDEHYDE; ALDOL REACTION; HOMOALLYL ALCOHOLS; LEWIS-ACIDS; ALLYLATION; ALLYLBORATION; RUTHENIUM;

D O I：

10.1021/jacs.6b01078

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Chiral iridium complexes modified by SEGPHOS catalyze the 2-propanol-mediated reductive coupling of branched allylic acetates 1a-1o with formaldehyde to form primary homoallylic alcohols 2a-2o with excellent control of regio- and enantioselectivity. These processes, which rely on enantiotopic pi-facial discrimination of sigma-allyliridium intermediates, represent the first examples of enantioselective formaldehyde C-C coupling beyond aldol addition.

引用

页码：3655 / 3658

页数：4

共 88 条

[1] Synthetic variations based on low-valent chromium:: new developments [J].

Avalos, M ;

Babiano, R ;

Cintas, P ;

Jiménez, JL ;

Palacios, JC .

CHEMICAL SOCIETY REVIEWS, 1999, 28 (03) :169-177

[2] [Cr(Salen)] as a 'bridge' between asymmetric catalysis, Lewis acids and redox processes [J].

Bandini, M ;

Cozzi, PG ;

Umani-Ronchi, A .

CHEMICAL COMMUNICATIONS, 2002, (09) :919-927

[3] The Mechanism and an Improved Asymmetric Allylboration of Ketones Catalyzed by Chiral Biphenols [J].

Barnett, David S. ;

Moquist, Philip N. ;

Schaus, Scott E. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (46) :8679-8682

[4] Divergent Regioselectivity in the Synthesis of Trisubstituted Allylic Alcohols by Nickel- and Ruthenium-Catalyzed Alkyne Hydrohydroxymethylation with Formaldehyde [J].

Bausch, Cory C. ;

Patman, Ryan L. ;

Breit, Bernhard ;

Krische, Michael J. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (25) :5686-5689

[5] Direct Enantioselective Organocatalytic Hydroxymethylation of Aldehydes Catalyzed by α,α-Diphenylprolinol Trimethylsilyl Ether [J].

Boeckman, Robert K., Jr. ;

Miller, John R. .

ORGANIC LETTERS, 2009, 11 (20) :4544-4547

[6] ASYMMETRIC CARBON CARBON BOND FORMATION VIA BETA-ALLYLDIISOPINOCAMPHEYLBORANE - SIMPLE SYNTHESIS OF SECONDARY HOMOALLYLIC ALCOHOLS WITH EXCELLENT ENANTIOMERIC PURITIES [J].

BROWN, HC ;

JADHAV, PK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (07) :2092-2093

[7] Asymmetric allyl- and crotylboration with the robust, versatile, and recyclable 10-TMS-9-borabicyclo[3.3.2]decanes [J].

Burgos, CH ;

Canales, E ;

Matos, K ;

Soderquist, JA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (22) :8044-8049

[8] Direct organocatalytic asymmetric α-hydroxymethylation of ketones and aldehydes [J].

Casas, J ;

Sundén, H ;

Córdova, A .

TETRAHEDRON LETTERS, 2004, 45 (32) :6117-6119

[9] DIPHOSPHINES WITH NATURAL BITE ANGLES NEAR 120-DEGREES INCREASE SELECTIVITY FOR NORMAL-ALDEHYDE FORMATION IN RHODIUM-CATALYZED HYDROFORMYLATION [J].

CASEY, CP ;

WHITEKER, GT ;

MELVILLE, MG ;

PETROVICH, LM ;

GAVNEY, JA ;

POWELL, DR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (14) :5535-5543

[10] Rhodium-Catalyzed Ketone Methylation Using Methanol Under Mild Conditions: Formation of α-Branched Products [J].

Chan, Louis K. M. ;

Poole, Darren L. ;

Shen, Di ;

Healy, Mark P. ;

Donohoe, Timothy J. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (03) :761-765

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