金属催化的对映选择性合成

Due to the chiral environment in living systems, taking the human body as the.example, optically active compounds with different absolute configurations show different biological activities. Thus, it is important to develop new methodologies which have the ability to enantioselectively construct a chiral center with the desired absolute configuration. The aim of this project is to develop new technology for chiral.synthesis with the desire to learn the beauty and originality of the chiral nature: (1) Starting from optically active functionalized allenes, we have been able to synthesize highly optically active butenolides, vinylic epoxides and α- or γ-amino.alcohols. For the synthesis of optically active allenes, we have applied resolution with chiral bases and enzyme-catalyzed kinetic resolution of the easily available racemic functionalized allenes..(2) A Pd(II)-catalyzed enantioselective cyclization of enynes affording.α-alkylidene-γ-lactones with ee up to 92% has been developed. (3) A Pd(II)-catalyzed intramolecular carbopalladation of a carbonyl or nitrile group has been developed with the potential of developing enantioselective catalytic.Grignard-type reaction for the synthesis of chiral alcohols..(4) The combined effect of axial chirality and point chirality in same ligands on new enantioselective catalytic reactions has been studied. New excellent ligands with.synergetical effect of different chiralities have been developed for the Pd(0)-catalyzed asymmetric allylation..(5) The first example of enantioselective addition of organozincs with aldehydes using a racemic ligand with the addition of optically active additives was observed.(6) With these new combinatorial approaches, enantioselective Diels-Alder with.a exceptionally efficient catalystic system was developed.(7) BINOL-skeleton derivated ligands have been successfully applied to Ln-catalyzed enantioselective reactions..(8) A N,N,N-ligand with psedeo C3-symmetry has been developed for the.enantioselective Lewis acid-catalyzed conjugate addition with >90% ee..Some of the results have been published in J. Am. Chem Soc. (5 times), Angew..Chem. (3 times), Org. Lett., J. Org. Chem. and Chem. Commun. etc. A comple of patents have been filed to protect the intellectual property.

手性现象广泛存在于自然界中，由于构成生命的三大基本物质：蛋白质、核酸和糖都是手性分子，所以手性药物的不同的光学异构体在生物体中的生理活性是不一样的。金属络合物由金属及配体两部分组成，在配体中引入手性中心，通过络合物结构的调谐发展对映选择性有机合成新反应是本项目的内容。本项目的开展将促进手性工业的发展和自然界手性现象认识.