Ti-catalyzed straightforward synthesis of exocyclic allenes

Chemistry : a European Journal
Juan Muñoz-BascónJ Enrique Oltra

Abstract

Exocyclic allenes constitute useful building blocks in organic synthesis and have recently been identified as key intermediates in the synthesis of natural products. Here the first general method for the most straightforward synthesis of exocyclic allenes reported to date is presented. This method is based on the Barbier-type cyclization of propargyl halides catalyzed by titanium; a safe, abundant, and ecofriendly metal. The reaction proceeds under mild conditions compatible with different functional groups and provides good yields of five-, six-, and seven-membered carbocycles and nitrogen-containing heterocycles bearing an exocyclic allene group. Experimental evidence supporting the proposed reaction mechanism is also provided. Moreover, this procedure can be carried out in an enantioselective manner by using chiral titanocene(III) catalysts. The utility of this method has been proved in the synthesis of the natural alkaloid stemoamide.

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Citations

Jul 16, 2014·The Journal of Organic Chemistry·Antonio RosalesJ Enrique Oltra
Jun 10, 2014·The Journal of Organic Chemistry·Benito AlcaideM Rosario Torres
Oct 27, 2015·Journal of the American Chemical Society·Jan StreuffDietmar A Plattner
Jan 26, 2017·Chemistry : a European Journal·Hideto MiyabeShigeru Kohtani
Sep 23, 2014·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Jan Streuff
Jan 8, 2019·Chemistry : a European Journal·Leonardus H LeijendekkerJan Streuff
Aug 26, 2016·Beilstein Journal of Organic Chemistry·Antonio Rosales, Ignacio Rodríguez-García
May 1, 2015·Angewandte Chemie·Andreas GansäuerRobert A Flowers
Nov 5, 2020·The Journal of Organic Chemistry·Antonio Rosales MartínezIgnacio Rodríguez-García
Dec 26, 2018·The Journal of Organic Chemistry·Josefa L López-MartínezMiriam Álvarez-Corral
Nov 29, 2017·Journal of the American Chemical Society·Makoto YoritateNoritaka Chida

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