Mechanistic studies on the catalytic asymmetric Mannich-type reaction with dihydroisoquinolines and development of oxidative Mannich-type reactions starting from tetrahydroisoquinolines

被引：98

作者：

Dubs, Christian ^{[1
]}

Hamashima, Yoshitaka ^{[1
]}

Sasamoto, Naoki ^{[1
]}

Seidel, Thomas M. ^{[1
]}

Suzuki, Shoko ^{[1
]}

Hashizume, Daisuke ^{[2
]}

Sodeoka, Mikiko ^{[1
]}

机构：

[1] RIKEN, Synthet Organ Chem Lab, Wako, Saitama 3510198, Japan

[2] RIKEN, Mol Characterizat Team, Wako, Saitama 3510198, Japan

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2008年 / 73卷 / 15期

关键词：

D O I：

10.1021/jo800800y

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Detailed mechanistic studies on our recently reported asymmetric addition reactions of malonates to dihydroisoquinolines (DHIQs) catalyzed by chiral Pd(II) complexes were carried out. It was found that an N,O-acetal was generated in situ by the reaction of DHIQ with (Boc)(2)O, and cooperative action of the Pd(II) complex as an acid-base catalyst allowed the formation of a chiral Pd enolate and a reactive iminium ion via alpha-fragmentation. The iminium ion was also accessible via oxidation with DDQ as an oxidant, and a catalytic asymmetric oxidative Mannich-type reaction was achieved with tetrahydroisoquinolines (THIQs) as starting materials. This oxidation protocol was applicable to N-acryloyl-protected THIQs, allowing the efficient synthesis of optically active tetrahydrobenzo[a]quinolizidine derivatives via intramolecular Michael reaction.

引用

页码：5859 / 5871

页数：13

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