Onizawa Yuji, Kusama Hiroyuki, Iwasawa Nobuharu
Department of Chemistry, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8551, Japan.
J Am Chem Soc. 2008 Jan 23;130(3):802-3. doi: 10.1021/ja0782605. Epub 2007 Dec 22.
When omega-acetylenic dienol silyl ethers containing NMs part in the tether were treated with a catalytic amount of W(CO)6 under photoirradiation, 2-azabicyclo[3.3.0]octanes were obtained in good yield via pi-alkyne complexes. On the other hand, treatment of the same substrates with a catalytic amount of W(CO)6 in the presence of n-Bu3N under the same reaction conditions gave 3-azabicyclo[3.3.0]octanes in good yield exclusively via vinylidene complexes. Thus, the pi-alkyne and vinylidene complex pathways are easily controlled by using a catalytic amount of W(CO)5(L) and an amine.
当含有连接链中NMs部分的ω-炔烯醇硅醚在光照射下用催化量的W(CO)6处理时，通过π-炔配合物以良好的产率得到2-氮杂双环[3.3.0]辛烷。另一方面，在相同反应条件下，在正丁基三氮存在下用催化量的W(CO)6处理相同底物，仅通过亚乙烯基配合物以良好的产率得到3-氮杂双环[3.3.0]辛烷。因此，通过使用催化量的W(CO)5(L)和胺可以容易地控制π-炔和亚乙烯基配合物途径。
