One-step synthesis of triethynylvinylmethanes and tetraethynylmethanes by GaCl(3)-promoted diethynylation of 1,4-enynes and 1,4-diynes

Ryo Amemiya; Katsunori Suwa; Junji Toriyama; Yoshio Nishimura; Masahiko Yamaguchi

doi:10.1021/ja051416l

One-step synthesis of triethynylvinylmethanes and tetraethynylmethanes by GaCl(3)-promoted diethynylation of 1,4-enynes and 1,4-diynes

J Am Chem Soc. 2005 Jun 15;127(23):8252-3. doi: 10.1021/ja051416l.

Authors

Ryo Amemiya¹, Katsunori Suwa, Junji Toriyama, Yoshio Nishimura, Masahiko Yamaguchi

Affiliation

¹ Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, Aoba, Sendai 980-8578, Japan.

PMID: 15941236
DOI: 10.1021/ja051416l

Abstract

The treatment of 1,4-enynes with chlorotriethylsilylacetylene at 130 degrees C in the presence of GaCl3 gave triethynylvinylmethanes by the diethynylation at the allylic methylene moiety. The addition of 2,6-di(tert-butyl)-4-methylpyridine and tert-butyldiphenylsilanol considerably improved the yields of the products by reducing the decompositions of the substrates and products. The reaction should involve the initial formation of allylgallium from the enynes and GaCl3, where GaCl3 activated hydrocarbon C-H to generate a nucleophilic organogallium intermediate. Carbometalation with chloroacetylene followed by beta-elimination then led to the ethynylated product. Triethynylvinylmethanes were obtained by the repeated regioselective ethynylation at the 3-position of the enynes. The reaction of allylsilanes with the chloroacetylene also gave diethynylvinylmethanes, in which 1,4-enynes were formed in situ by the addition-elimination of allylgallium formed from allylsilane and GaCl3. Tetraethynylmethanes were obtained by reacting 1,4-diynes with the chloroacetylene at 150 degrees C. The structure and amount of silanol can be used to control the reactivity of GaCl3.