Catalytic asymmetric rearrangement of allylic N-aryl trifluoroacetimidates.: A useful method for transforming prochiral allylic alcohols to chiral allylic amines

被引：153

作者：

Overman, LE

Owen, CE

Pavan, MM

Richards, CJ

机构：

[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

[2] Univ London Queen Mary Coll, Dept Chem, London E1 4NS, England

来源：

ORGANIC LETTERS | 2003年 / 5卷 / 11期

关键词：

D O I：

10.1021/ol0271786

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A useful method for the conversion of prochiral allylic alcohols to chiral allylic amines of high enantiopurity is reported. N-(4-Methoxyphenyl)-trifluoroacetimidates; are excellent substrates for the palladium(II)-catalyzed allylic imidate rearrangement as the allylic trifluoroacetamide products can be deprotected in two steps to provide chiral nonracemic allylic amines. Di-mu-chlorobis[(eta(5)-(S)-(pR)-2-(2'-(4'-isopropyl))oxazolinylcyclo-pentadienyl, 1-C,3'-N))(eta(4)-tetraphenylcyclobutadiene)cobalt]dipalladium (6a, COP-CI) is a superior catalyst because it does not require activation with silver salts and provides rearranged allylic trifluoroacetamides in good yields and high enantiomeric purities.

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页码：1809 / 1812

页数：4

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共 21 条

[1] First enantioselective catalyst for the rearrangement of allylic imidates to allylic amides [J].

Calter, M ;

Hollis, TK ;

Overman, LE ;

Ziller, J ;

Zipp, GG .

JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (05) :1449-1456

[2] Planar-chiral cyclopalladated ferrocenyl amines and imines as enantioselective catalysts for allylic imidate rearrangements [J].

Cohen, F ;

Overman, LE .

TETRAHEDRON-ASYMMETRY, 1998, 9 (18) :3213-3222

[3] High enantioselection in the rearrangement of allylic imidates with ferrocenyl oxazoline catalysts [J].

Donde, Y ;

Overman, LE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (12) :2933-2934

[4] Palladium catalyzed enantioselective rearrangement of allylic imidates to allylic amides [J].

Hollis, TK ;

Overman, LE .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1999, 576 (1-2) :290-299

[5] Cyclopalladated ferrocenyl amines as enantioselective catalysts for the rearrangement of allylic imidates to allylic amides [J].

Hollis, TK ;

Overman, LE .

TETRAHEDRON LETTERS, 1997, 38 (51) :8837-8840

[6] PALLADIUM(II)-CATALYZED ASYMMETRIC CYCLIZATION OF 2-ALLYLPHENOLS BY USE OF OPTICALLY-ACTIVE BETA-PINENE [J].

HOSOKAWA, T ;

MIYAGI, S ;

MURAHASHI, SI ;

SONODA, A .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1978, (16) :687-688

[7] The first tridentate ligand for catalytic enantioselective aza-Claisen rearrangement of allylic imidates [J].

Jiang, YT ;

Longmire, JM ;

Zhang, XM .

TETRAHEDRON LETTERS, 1999, 40 (08) :1449-1450

[8] Metallocene-appended imidazoles displaying virtual planar chirality [J].

Jones, G ;

Richards, CJ .

ORGANOMETALLICS, 2001, 20 (06) :1251-1254

[9] The effect of face-blocking in the enantioselective aza-Claisen rearrangement of allylic imidates [J].

Kang, J ;

Kim, TH ;

Yew, KH ;

Lee, WK .

TETRAHEDRON-ASYMMETRY, 2003, 14 (04) :415-418

[10] Preparation of bis(palladacycles) and application to asymmetric aza-Claisen rearrangement of allylic imidates [J].

Kang, J ;

Yew, KH ;

Kim, TH ;

Choi, DH .

TETRAHEDRON LETTERS, 2002, 43 (52) :9509-9512