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
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
收藏
页码:3655 / 3658
页数:4
相关论文
共 88 条
[41]   Advances in ruthenium catalysis.: Novel catalytic reactions via η3-allylruthenium intermediates [J].
Kondo, T ;
Mitsudo, T .
CURRENT ORGANIC CHEMISTRY, 2002, 6 (13) :1163-1179
[42]   NEW DIPHOSPHINE LIGANDS BASED ON HETEROCYCLIC AROMATICS INDUCING VERY HIGH REGIOSELECTIVITY IN RHODIUM-CATALYZED HYDROFORMYLATION - EFFECT OF THE BITE ANGLE [J].
KRANENBURG, M ;
VANDERBURGT, YEM ;
KAMER, PCJ ;
VANLEEUWEN, PWNM ;
GOUBITZ, K ;
FRAANJE, J .
ORGANOMETALLICS, 1995, 14 (06) :3081-3089
[43]   Asymmetric aldol reaction of 2-cyanopropionates catalysed by trans-chelating chiral diphosphine ligand TRAP-rhodium(I) complex [J].
Kuwano, R ;
Miyazaki, H ;
Ito, Y .
CHEMICAL COMMUNICATIONS, 1998, (01) :71-72
[44]   Scandium-catalyzed allylboration of aldehydes as a practical method for highly diastereo- and enantioselective construction of homoallylic alcohols [J].
Lachance, H ;
Lu, XS ;
Gravel, M ;
Hall, DG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (34) :10160-10161
[45]  
Lachance H., 2008, Org. React, V73, P1
[46]   CHIRAL PHOSPHANODIHYDROOXAZOLES IN ASYMMETRIC CATALYSIS - TUNGSTEN-CATALYZED ALLYLIC SUBSTITUTION [J].
LLOYDJONES, GC ;
PFALTZ, A .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1995, 34 (04) :462-464
[47]   Asymmetric allylboration of ketones catalyzed by chiral diols [J].
Lou, Sha ;
Moquist, Philip N. ;
Schaus, Scott E. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (39) :12660-12661
[48]   Lewis acid-catalyzed asymmetric hydroxymethylation of silicon enolates in aqueous media [J].
Manabe, K ;
Ishikawa, S ;
Hamada, T ;
Kobayashi, S .
TETRAHEDRON, 2003, 59 (52) :10439-10444
[49]   Creation of quaternary stereocenters in carbonyl allylation reactions [J].
Marek, Ilan ;
Sklute, Genia .
CHEMICAL COMMUNICATIONS, 2007, (17) :1683-1691
[50]   Organocatalytic α-hydroxymethylation of cyclopentanone with aqueous formaldehyde: Easy access to chiral δ-lactones [J].
Mase, Nobuyuki ;
Inoue, Azusa ;
Nishio, Masaki ;
Takabe, Kunihiko .
BIOORGANIC & MEDICINAL CHEMISTRY LETTERS, 2009, 19 (14) :3955-3958