铑（I）催化芳基硼酸对N-叔丁基亚磺酰基和N-二苯基磷酰基醛亚胺的非对映选择性和对映选择性加成反应。

Diastereoselective and enantioselective Rh(I)-catalyzed additions of arylboronic acids to N-tert-butanesulfinyl and N-diphenylphosphinoyl aldimines.

作者信息

Weix Daniel J, Shi Yili, Ellman Jonathan A

机构信息

Center for New Directions in Organic Synthesis, Department of Chemistry, University of California, Berkeley, California 94720, USA.

出版信息

J Am Chem Soc. 2005 Feb 2;127(4):1092-3. doi: 10.1021/ja044003d.

DOI:10.1021/ja044003d

PMID:15669835

Abstract

Two new Rh(I)-catalyzed methods for the synthesis of chiral alpha-branched amines via addition of arylboronic acids to N-tert-butanesulfinyl and N-diphenylphosphinoyl imines have been developed. The syntheses are more functional group tolerant than alternative methods utilizing Grignard or organolithium reagents, and the imine activating groups used are easily removed. These methods are both high-yielding (70-97% yield) and very selective (>93:7 dr and 88-94% ee). Significantly, the N-tert-butanesulfinyl imine method works for aliphatic imines with enolizable protons. In addition, a one-pot procedure for the synthesis of N-tert-butanesulfinyl protected alpha-branched amines from aldehydes has been developed.

摘要

已开发出两种新的铑（I）催化方法，通过将芳基硼酸加成到N-叔丁基亚磺酰基和N-二苯基膦酰基亚胺上来合成手性α-支链胺。与使用格氏试剂或有机锂试剂的替代方法相比，这些合成方法对官能团的耐受性更强，并且所使用的亚胺活化基团易于去除。这些方法产率都很高（70-97%产率）且选择性非常好（>93:7的非对映体比例和88-94%的对映体过量）。值得注意的是，N-叔丁基亚磺酰基亚胺方法适用于具有可烯醇化质子的脂肪族亚胺。此外，还开发了一种从醛一锅法合成N-叔丁基亚磺酰基保护的α-支链胺的方法。