Enantioselective synthesis of pyrrolidine-, piperidine-, and azepane-type N-heterocycles with α-alkenyl substitution: the CpRu-catalyzed dehydrative intramolecular N-allylation approach.
Enantioselective synthesis of pyrrolidine-, piperidine-, and azepane-type N-heterocycles with α-alkenyl substitution: the CpRu-catalyzed dehydrative intramolecular N-allylation approach.
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DOI：
10.1021/ol203218d
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发表时间：
2012-01
期刊：
影响因子：
5.2
通讯作者：
T. Seki;Shinji Tanaka;M. Kitamura
中科院分区：
文献类型：
--
作者：
T. Seki;Shinji Tanaka;M. Kitamura
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)]催化n -取代ω-氨基和-氨基羰基烯丙醇的不对称脱水n -烯丙基化，底物/催化剂比高达2000，得到α-烯基吡咯烷-、哌啶-和氮杂环，对映体比高达bbb99:1。广泛适用的n取代，包括Boc， Cbz, Ac, Bz，丙烯酰，巴豆醇，甲酰基和Ts，极大地促进了对天然产物合成的进一步操作。
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.