Ellman Jonathan A, Owens Timothy D, Tang Tony P
Center for New Directions in Organic Synthesis, Department of Chemistry, University of California, Berkeley, California 94720-1460,USA.
Acc Chem Res. 2002 Nov;35(11):984-95. doi: 10.1021/ar020066u.
N-tert-Butanesulfinyl aldimines 3 and ketimines 4 are exceedingly versatile intermediates for the asymmetric synthesis of amines. The N-tert-butanesulfinyl imines are prepared in high yields by condensing enantiomerically pure tert-butanesulfinamide 1, which is readily available in either configuration, with a wide range of aldehydes and ketones. The tert-butanesulfinyl group activates the imines for the addition of many different classes of nucleophiles, serves as a powerful chiral directing group, and after nucleophilic addition is readily cleaved by treatment of the product with acid. A wide range of highly enantioenriched amines, including alpha-branched and alpha,alpha-dibranched amines, alpha- and beta-amino acids, 1,2- and 1,3-amino alcohols, and alpha-trifluoromethyl amines, are efficiently synthesized using this methodology. In addition, N-tert-butanesulfinyl imine derivatives provide a new family of ligands for asymmetric catalysis.
N-叔丁基亚磺酰基醛亚胺3和酮亚胺4是用于胺类不对称合成的极为通用的中间体。通过将对映体纯的叔丁基亚磺酰胺1(两种构型均可方便获得)与多种醛和酮缩合,可高产率制备N-叔丁基亚磺酰基亚胺。叔丁基亚磺酰基可活化亚胺以便添加许多不同种类的亲核试剂,作为强大的手性导向基团,并且在亲核加成后,通过用酸处理产物可容易地将其裂解。使用该方法可高效合成多种高度对映体富集的胺,包括α-支链和α,α-二支链胺、α-和β-氨基酸、1,2-和1,3-氨基醇以及α-三氟甲基胺。此外,N-叔丁基亚磺酰基亚胺衍生物为不对称催化提供了一类新的配体。