Research Center for Materials Science and the Department of Chemistry, Nagoya University, Chikusa, Nagoya 464-8602, Japan.
Org Lett. 2012 Jan 20;14(2):608-11. doi: 10.1021/ol203218d. Epub 2011 Dec 23.
A cationic CpRu complex of chiral picolinic acid derivatives [(R)- or (S)-Cl-Naph-PyCOOCH(2)CH═CH(2)] catalyzes asymmetric intramolecular dehydrative N-allylation of N-substituted ω-amino- and -aminocarbonyl allylic alcohols with a substrate/catalyst ratio of up to 2000 to give α-alkenyl pyrrolidine-, piperidine-, and azepane-type N-heterocycles with an enantiomer ratio of up to >99:1. The wide range of applicable N-substitutions, including Boc, Cbz, Ac, Bz, acryloyl, crotonoyl, formyl, and Ts, significantly facilitates further manipulation toward natural product synthesis.
手性吡啶酸衍生物的阳离子 CpRu 配合物[(R)-或(S)-Cl-Naph-PyCOOCH(2)CH═CH(2)]可以催化非对称的分子内脱水 N-烯丙基化反应，反应底物与催化剂的比例高达 2000，对 N-取代的ω-氨基-和-氨基羰基烯丙醇进行反应，生成的α-烯基吡咯烷、哌啶和氮杂环庚烷型 N-杂环化合物的对映体比例高达＞99:1。适用的 N-取代基范围广泛，包括 Boc、Cbz、Ac、Bz、丙烯酰基、巴豆酰基、甲酰基和 Ts，这极大地方便了进一步用于天然产物的合成。
