Highly Enantioselective Reactions and Asymmetric Synthesis of Biologically Active Compounds

(1)Rh_2（S-TCPTTL）_4是2-重氮-3，6-二酮酯与芳基乙炔、烷氧基乙炔和苯乙烯偶极亲电试剂的对映选择性串联羰基叶立德形成-环加成反应的一种非常有效的催化剂，其环加成产物的产率高，对映选择性高达99%ee，对苯乙烯的外消旋非对映选择性也很好。(2)通过含铑（II）配合物的单体与苯乙烯和柔性交联剂的共聚，实现了Rh_2（S-PTTL）_4的高效固定化。固定化催化剂在-78℃下促进了分子内C-H插入反应，具有较高的对映选择性，可连续使用100次，浸出量低（0.28ppm）。(3)在1mol%Rh_2（S-BPTPI）_4的作用下，Rawal二烯与醛发生杂Diels-桤木反应，经乙酰氯处理后，可得到相应的二氢吡喃酮，ee值高达99%。

(1) Rh_2(S-TCPTTL)_4 is an exceptionally effective catalyst for enantioselective tandem carbonyl ylide formation-cycloaddition reactions of 2-diazo-3,6-diketoesters with arylacetylene, alkoxyacetylene, and styrene dipolarophiles, providing cycloadducts in good to high yields and with enantioselectivities of up to 99% ee as well as with perfect exo diastereoselectivity for styrenes.(2) A highly effective immobilization of Rh_2(S-PTTL)_4 has been achieved by copolymerization of dirhodium(II) complex-containing monomer with styrene and a flexible cross-linker. The immobilized catalyst promoted the intramolecular C-H insertion reaction at -78℃ with high enantioselectivity, and could be used for up to 100 sequential applications with a low leaching level (0.28 ppm).(3) The hetero-Diels-Alder reaction between Rawal's diene and aldehydes under the influence of 1 mol % of Rh_2(S-BPTPI)_4 proceeded cleanly and gave, after treatment with acetyl chloride, the corresponding dihydropyranones in up to 99% ee.