Confined acids catalyze asymmetric single aldolizations of acetaldehyde enolates

被引：70

作者：

Schreyer, Lucas ^{[1
]}

Kaib, Philip S. J. ^{[1
]}

Wakchaure, Vijay N. ^{[1
]}

Obradors, Carla ^{[1
]}

Properzi, Roberta ^{[1
]}

Lee, Sunggi ^{[1
]}

List, Benjamin ^{[1
]}

机构：

[1] Max Planck Inst Kohlenforsch, Kaiser Wilhelm Pl 1, D-45470 Mulheim, Germany

来源：

SCIENCE | 2018年 / 362卷 / 6411期

基金：

欧洲研究理事会;

关键词：

CROSSED-ALDOL REACTION; ALDEHYDES; METHYL;

D O I：

10.1126/science.aau0817

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Reactions that form a product with the same reactive functionality as that of one of the starting compounds frequently end in oligomerization. As a salient example, selective aldol coupling of the smallest, though arguably most useful, enolizable aldehyde, acetaldehyde, with just one partner substrate has proven to be extremely challenging. Here, we report a highly enantioselective Mukaiyama aldol reaction with the simple triethylsilyl (TES) and tert-butyldimethylsilyl (TBS) enolates of acetaldehyde and various aliphatic and aromatic acceptor aldehydes. The reaction is catalyzed by recently developed, strongly acidic imidodiphosphorimidates (IDPi), which, like enzymes, display a confined active site but, like small-molecule catalysts, have a broad substrate scope. The process is scalable, fast, efficient (0.5 to 1.5 mole % catalyst loading), and greatly simplifies access to highly valuable silylated acetaldehyde aldols.

引用

页码：216 / 219

页数：4

共 30 条

[11] A Powerful Chiral Counteranion Motif for Asymmetric Catalysis [J].

Garcia-Garcia, Pilar ;

Lay, Frank ;

Garcia-Garcia, Patricia ;

Rabalakos, Constantinos ;

List, Benjamin .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (24) :4363-4366

[12] The Catalytic Asymmetric Mukaiyama-Michael Reaction of Silyl Ketene Acetals with α,β-Unsaturated Methyl Esters [J].

Gatzenmeier, Tim ;

Kaib, Philip S. J. ;

Lingnau, Julia B. ;

Goddard, Richard ;

List, Benjamin .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2018, 57 (09) :2464-2468

[13] A diarylprolinol in an asymmetric, catalytic, and direct crossed-aldol reaction of acetaldehyde [J].

Hayashi, Yujiro ;

Itoh, Takahiko ;

Aratake, Seiji ;

Ishikawa, Hayato .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (11) :2082-2084

[14] Chiral Primary Amine Catalyzed Asymmetric Direct Cross-Aldol Reaction of Acetaldehyde [J].

Hu, Shenshen ;

Zhang, Long ;

Li, Jiuyuan ;

Luo, Sanzhong ;

Cheng, Jin-Pei .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2011, 2011 (18) :3347-3352

[15] Extremely Active Organocatalysts Enable a Highly Enantioselective Addition of Allyltrimethylsilane to Aldehydes [J].

Kaib, Philip S. J. ;

Schreyer, Lucas ;

Lee, Sunggi ;

Properzi, Roberta ;

List, Benjamin .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (42) :13200-13203

[16] syn-selective and enantioselective direct cross-aldol reactions between aldehydes catalyzed by an axially chiral amino sulfonamide [J].

Kano, Taichi ;

Yamaguchi, Yukako ;

Tanaka, Youhei ;

Maruoka, Keiji .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (10) :1738-1740

[17] Polyketide stereotetrads in natural products [J].

Koskinen, AMP ;

Karisalmi, K .

CHEMICAL SOCIETY REVIEWS, 2005, 34 (08) :677-690

[18] Asymmetric Catalysis via Cyclic, Aliphatic Oxocarbenium Ions [J].

Lee, Sunggi ;

Kaib, Philip S. J. ;

List, Benjamin .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (06) :2156-2159

[19] Catalytic Asymmetric [4+2]-Cycloaddition of Dienes with Aldehydes [J].

Liu, Luping ;

Kim, Hyejin ;

Xie, Youwei ;

Fares, Christophe ;

Kaib, Philip S. J. ;

Goddard, Richard ;

List, Benjamin .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (39) :13656-13659

[20] Synthetic Studies Towards the Synthesis of 6-Substituted 3-Fluoro-5,6-dihydropyran-2-ones [J].

Mandal, Samir K. ;

Sarkar, Apurba ;

Chakraborty, Puskin ;

Chattopadhyay, Ashoke P. .

SYNLETT, 2018, 29 (01) :75-78

← 1 2 3 →