Lurain Alice E, Maestri Aaron, Kelly Ann Rowley, Carroll Patrick J, Walsh Patrick J
P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
J Am Chem Soc. 2004 Oct 27;126(42):13608-9. doi: 10.1021/ja046750g.
Two highly enantio- and diastereoselective one-pot procedures for the synthesis of epoxy alcohols with up to three contiguous stereocenters are reported. Route one involves asymmetric addition of an alkylzinc reagent to an enal followed by diastereoselective epoxidation. Route two entails asymmetric vinylation of an aldehyde with divinylzinc reagents and subsequent diastereoselective epoxidation. The oxidant for the epoxidation is generated by exposure of the allylic alkoxide intermediate and the remaining organozinc reagent to dioxygen. Upon addition of catalytic titanium tetraisopropoxide, the directed epoxidation yields the epoxy alcohols with good to excellent yields.
报道了两种高度对映选择性和非对映选择性的一锅法合成具有多达三个相邻立体中心的环氧化醇的方法。路线一包括将烷基锌试剂不对称加成到烯醛上，然后进行非对映选择性环氧化。路线二需要用二乙烯基锌试剂使醛不对称乙烯基化，随后进行非对映选择性环氧化。环氧化的氧化剂是通过烯丙醇盐中间体和剩余的有机锌试剂暴露于氧气中产生的。加入催化量的四异丙醇钛后，定向环氧化以良好至优异的产率得到环氧化醇。
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