Ligand controlled highly regio- and enantioselective synthesis of α-acyloxyketones by palladium-catalyzed allylic alkylation of 1,2-enediol carbonates

被引：62
作者：
Trost, Barry M. [1 ]
Xu, Jiayi [1 ]
Schmidt, Thomas [1 ]
机构：
[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2008年 / 130卷 / 36期
基金：
美国国家卫生研究院; 美国国家科学基金会;
关键词：
D O I：
10.1021/ja8038954
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The palladium catalyzed decarboxylative asymmetric allylic alkylation of allyl 1,2-enediol carbonates 1 can decompose to either α-hydroxyketones 3 or α-hydroxyaldehydes 4. The product distribution is largely controlled by the ligand. Using Lnaph in DME we exclusively obtained the ketone product in good to excellent yields and high enantiomeric excesses. The reaction proceeds under extremely mild conditions, so we can have a broad range of choices of OR. Besides the commonly used protection groups such as OAc and OPiv, a more functionalized group such as methyl but-2-enoyl group can also be used, downstream process of which can afford other synthetically interesting structures. Copyright © 2008 American Chemical Society.
引用
收藏
页码：11852 / 11853
页数：2
相关论文
共 36 条
[11]  
Davis F. A., 1995, HOUBEN WEYL METHODS, VE21e, P4497
[12]   ASYMMETRIC HYDROXYLATION OF ENOLATES WITH N-SULFONYLOXAZIRIDINES [J].
DAVIS, FA ;
CHEN, BC .
CHEMICAL REVIEWS, 1992, 92 (05) :919-934
[13]   Enantioselective alkylation of acyclic α,α-disubstituted tributyltin enolates catalyzed by a {Cr(salen)) complex [J].
Doyle, Abigail G. ;
Jacobsen, Eric N. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (20) :3701-3705
[14]  
Enders D, 2002, ANGEW CHEM INT EDIT, V41, P1743, DOI 10.1002/1521-3773(20020517)41:10<1743::AID-ANIE1743>3.0.CO
[15]  
2-Q
[16]   Iridium-catalyzed regio- and enantioselective allylation of ketone enolates [J].
Graening, T ;
Hartwig, JF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (49) :17192-17193
[17]   ALPHA-HYDROXY KETONES IN HIGH ENANTIOMERIC PURITY FROM ASYMMETRIC DIHYDROXYLATION OF ENOL ETHERS [J].
HASHIYAMA, T ;
MORIKAWA, K ;
SHARPLESS, KB .
JOURNAL OF ORGANIC CHEMISTRY, 1992, 57 (19) :5067-5068
[18]   Direct proline-catalyzed asymmetric α-aminoxylation of ketones [J].
Hayashi, Y ;
Yamaguchi, J ;
Sumiya, T ;
Shoji, M .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (09) :1112-1115
[19]   Ir-catalyzed regio- and enantioselective decarboxylative allylic Alkylations [J].
He, Hu ;
Zheng, Xiao-Jian ;
Li, Yi ;
Dai, Li-Xin ;
You, Shu-Li .
ORGANIC LETTERS, 2007, 9 (21) :4339-4341
[20]   Stereoselective synthesis of optically active α-hydroxy ketones and anti-1,2-diols via asymmetric transfer hydrogenation of unsymmetrically substituted 1,2-diketones [J].
Koike, T ;
Murata, K ;
Ikariya, T .
ORGANIC LETTERS, 2000, 2 (24) :3833-3836
1234