New Methodology for the Construction of Asymmetric Carbon Skeletons Utilizing the Chirality of Hetero Atoms

A)在超高压下进行了各种手性亚磺酰基苯的Diels-Alder反应。在大多数情况下，与低活性双烯(如呋喃)的反应提供了相当高的非对映选择性的环加合物。B)研究了(RS)-马来酸亚磺酯与各种亲偶极分子的不对称1，3-偶极环加成反应，并提出了配对概念以扩展良好的非对映选择性。顺丁烯二酸酯与2，3，4，5-四氢吡啶-1-氧化物很好地结合在一起，得到了两个具有良好非对映选择性的环加合物。c)合成了以2-外羟基-10-龙脑基为亚磺基的手性亚磺基乙烯。这些亚磺酰二烯基化合物以高度的非对映选择性影响Diels-Alder反应。特别是在常规条件下，手性α-亚磺酰马来酰亚胺很容易与反应活性较低的Diels-Alder二烯如呋喃反应生成相应的环加合物。将这些不对称的Diels-Alder反应应用于吲哚里西定和吡咯里西丁生物碱的手性合成。d)发展了以2-外羟基-10-龙脑基为手性配体制备光学活性硒氧化物的新方法。用于制备新型手性硒基亲二烯化合物的方法的应用正在进行中。

a) The Diels-Alder reaction of various chiral sulfinyl eghenes under ultra-high pressure has been carried out. In most cases, the reaction with low reactive dienes such as furans afforded the cycloadducts in fairly high diastereoselectivity. Effective methodology for the construction of asymmetric carbon skeletons under atmospheric and ultra-high pressure is being developed.b) Asymmetric 1,3-dipolar cycloaddition of (RS)-sulfinylmaleate with various dipolarophiles has been studied and matched-pair concept has been proposed for the abtention of good diastereoselectivity. The maleate made a good combination with 2,3,4,5-tetrahydropyridine 1-oxide to give two cycloadducts with excellent diastereoselectivity.c) Synthesis of chiral sulfinylethenes which have a 2-exo-hydroxy-10-bornyl group as the sulfinyl ligand has been studied. These sulfinyl dienophiles effected Diels-Alder reactions with a high degree of diastereoselectivity. Especially, the chiral alfa-sulfinylmaleimides readily reacted with Diels-Alder dienes with rather low reactivities such as furan, to give the corresponding cycl oadducts under conventional conditions. Application of these asymmetric Diels-Alder reactions to the chiral synthesis of indolizidine- and pyrrolizidine-alkaloids has been accomplished.d) The new methodology for the preparation of optically active selenoxides using 2-exo-hydroxy-10-bornyl group as a chiral ligand has been developed. Application of the methodology for the preparation of novel chiral seleninyl dienophiles is under way.