Development of asymmetric reactions using multi-reagent complexes

1)在锂酰胺的存在下，将手性醋酸酯衍生的手性烯酸锂不对称加成到N-PMP亚胺中，通过氧化产生的dianion，立体选择性地高收率合成了紫杉醇侧链前体。2)采用手性配体控制芳基锂与烯酸酯的串联共轭加成-环化反应，实现了(-)-1-脱氧石蒜碱的正式全合成。3)采用偕胺磷铑催化芳硼烷试剂在取代环己酮上不对称加成，合成了立体选择性高的5-芳基环己酮和反式3,6-二取代环己酮。4)研究了手性氨基醇控制的烷基锌与硝基烯和醛的不对称加成反应。5)开发了手性恶唑啉配体控制的催化不对称分子内氢胺化反应。6)研究了手性氨基膦配体控制的二烷基锌与硝基烯烃的不对称加成反应。7)采用手性二醚配体控制的串联Michael加成-烷基化工艺，实现了(+)-氯的形式化合成。

1)A precursor of Taxol side chain was stereoselectively synthesized in high yield by the oxidation of the dianion resulting from the asymmetric addition of a chiral lithium enolate, derived from a chiral acetate, to N-PMP imine in the presence of a lithum amide.2)A formal total synthesis of (-)-1-deoxylycorine was achieved using tandem conjugate addition-cyclization reaction of aryllithium and alkenoate controled by a chiral ligand.3)5-Arylcyclohexenones and trans-3,6-disubstituted cyclohexanons were synthesized with high stereoselectivity in good yields using an amidophosphane-rhodium catalyzed asymmetric addition of arylborane reagents to substituted cyclohexenones.4)Chiral amino alcohol controlled asymmetric addition of alkynylzincs to nitroalkenes and aldehydes was developed.5)Chiral oxazoline ligand controlled catalytic asymmetric intramolecular hydroamination was developed.6)Chiral amidophosphane ligand controlled asymmetric addition of dialkylzincs to nitroalkene was developed.7)A formal synthesis of (+)-halichlorine was achieved using tandem Michael addition-alkylation protocol controlled by a chiral diether ligand.