320400-12-2Relevant academic research and scientific papers
Acid-catalyzed cyclization of vinylsilanes bearing a hydroxy group: A new method for stereoselective synthesis of disubstituted tetrahydrofurans
Miura,Okajima,Hondo,Nakagawa,Takahashi,Hosomi
, p. 11348 - 11357 (2007/10/03)
In the presence of a catalytic amount of TsOH or TiCl4, (Z)-5-silyl-4-penten-1-ols ((Z)-1) are smoothly cyclized to 2-silylmethyl-substituted tetrahydrofurans. This cyclization is applicable to the construction of a tetrahydropyran ring. The silyl group and the geometry of the C-C double bond strongly influence the cychzation rate. TBDMS and benzyldimethylsilyl groups considerably accelerate the cyclization in comparison with a dimethylphenylsilyl group, and (E)-vinylsilanes show much lower reactivity than the corresponding (Z)-isomers. The cyclization proceeds by stereospecific syn addition of the hydroxy group. Vinylsilanes 17, 19, and 21, (Z)-5-silyl-4-penten-1-ols bearing a substituent on the methylene tether, smoothly undergo the acid-catalyzed cyclization to give trans-2,5-, cis-2,4-, and trans-2,3-disubstituted tetrahydrofurans, respectively, with moderate to high stereoselectivity. The silyl group of some cychzed products can be easily converted into a hydroxy group with stereochemical retention.
