Highly efficient asymmetric hydrogenation of 2-methylenesuccinamic acid using a Rh-DuPHOS catalyst

被引：32

作者：

Cobley, CJ ^{[1
]}

Lennon, IC ^{[1
]}

Praquin, C ^{[1
]}

Zanotti-Gerosa, A ^{[1
]}

Appell, RB ^{[1
]}

Goralski, CT ^{[1
]}

Sutterer, AC ^{[1
]}

机构：

[1] Dow Chem Co USA, Dowpharma, Cambridge CB4 0WG, England

来源：

ORGANIC PROCESS RESEARCH & DEVELOPMENT | 2003年 / 7卷 / 03期

关键词：

D O I：

10.1021/op0256183

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

An extremely efficient route to highly enantiomerically enriched 2-methylsuccinamic acid via asymmetric hydrogenation has been developed. By using [(SS)-Et-DuPHOS Rh COD]BF4 as the precatalyst under a set of broadly optimised process parameters, (R)-2-methylsuccinamic acid was obtained in 96% ee at a substrate-to-catalyst ratio (S/C) of 100000 (average turnover frequency similar to13000 h-1). The exclusion of chloride-containing contaminants in the substrate was found to be crucial in obtaining exceptionally low catalyst loadings. This material could be upgraded with a single-crystal digestion to yield (R)2-methylsuccinamic acid in > 99.5% ee containing less than 1 ppm rhodium.

引用

页码：407 / 411

页数：5

共 18 条

[1] THE ABSOLUTE CONFIGURATION OF THE C1-ATOM IN RETRONECANONE (1-METHYL-7-OXOPYRROLIZIDINE) [J].

ADAMS, R ;

FLES, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1959, 81 (18) :4946-4951

[2]

Berens U, 2000, ANGEW CHEM INT EDIT, V39, P1981, DOI 10.1002/1521-3773(20000602)39:11<1981::AID-ANIE1981>3.0.CO

[3]

2-3

[4] Enantioselective catalysis in fine chemicals production [J].

Blaser, HU ;

Spindler, F ;

Studer, A .

APPLIED CATALYSIS A-GENERAL, 2001, 221 (1-2) :119-143

[5] Modular phospholane ligands in asymmetric catalysis [J].

Burk, MJ .

ACCOUNTS OF CHEMICAL RESEARCH, 2000, 33 (06) :363-372

[6] NEW CHIRAL 1,1'-BIS(PHOSPHOLANO)FERROCENE LIGANDS FOR ASYMMETRIC CATALYSIS [J].

BURK, MJ ;

GROSS, MF .

TETRAHEDRON LETTERS, 1994, 35 (50) :9363-9366

[7]

Burk MJ, 1998, ANGEW CHEM INT EDIT, V37, P1931, DOI 10.1002/(SICI)1521-3773(19980803)37:13/14<1931::AID-ANIE1931>3.0.CO

[8]

2-3

[9] Me-DuPHOS-Rh-catalyzed asymmetric synthesis of the pivotal glutarate intermediate for candoxatril [J].

Burk, MJ ;

Bienewald, F ;

Challenger, S ;

Derrick, A ;

Ramsden, JA .

JOURNAL OF ORGANIC CHEMISTRY, 1999, 64 (09) :3290-3298

[10]

FUJI T, 1972, TETRAHEDRON LETT, V13, P3075

← 1 2 →