Convenient Methods for Synthesis of C ₂-Symmetric Diphenyltetrahydro­thiophenes

Abstract

Racemic and optically pure (-)-(3R,4R)-3,4-diphenyltetrahydrothiophene, (+)-(2S,5S)-2,5-diphenyltetrahydrothiophene, and (-)-(3S,6S)-3,6-diphenyl-1,2-dithiane were synthesized by use, in the crucial steps, of the easy-to-handle borane systems tetra­butylammonium borohydride-iodine and tetrabutylammonium borohydride-iodomethane.

diphenyltetrahydrothiophenes - 3,6-diphenyl-1,2-dithiane - asymmetric reduction - tetrabutylammonium borohydride - sulfur heterocycles

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For compounds 1, 2, and 3, diffraction data were collected on a Bruker SMART APEX CCD area detector system using graphite monochromated Mo Kα radiation (λ = 0.71073 Å). Data reduction was carried out with SAINTPLUS, and the structures were solved and refined with SHELXS-97. All non-hydrogen atoms were refined anisotropically.
Crystal data for 1 (CCDC 711632): C₁₆H₁₆S, MW = 240.36, monoclinic, space group: P21, a = 10.363 (2) Å, b = 8.6732 (19) Å, c = 14.857 (3) Å, β = 91.314 (4)˚, V = 1335.0(5) Å^³, Z = 4, ρ = 1.196 Mg˙M^-³, µ = 0.218 mm^-¹, T = 298 (2) K. Of the 13820 reflections collected, 5194 were unique (R _int = 0.0301). Refinement on all data converged at R1 = 0.0487, wR2 = 0.1107.
Crystal data for 2 (CCDC 711633): C₁₆H₁₆S, MW = 240.35, monoclinic, space group: P21, a = 13.453 (4) Å, b = 5.7139 (18) Å, c = 17.416 (5) Å, β = 99.656 (5)˚, V = 1319.8 (7) Å^³, Z = 4, ρ = 1.210 Mg˙M^-³, µ = 0.220 mm^-¹, T = 298 (2) K. Of the 12428 reflections collected, 4612 were unique (R _int = 0.0626). Refinement on all data converged at R1 = 0.0750, wR2 = 0.1969.
Crystal data for 3 (CCDC 711634): C₁₆H₁₆S₂, MW = 272.41, trigonal, space group: P3₁21, a = 9.2159 (14) Å, b = 9.2159 (14) Å, c = 14.647 (5) Å, α = 90˚, β = 90˚, γ = 120˚, V = 1077.3 (4) Å^³, Z = 3, ρ = 1.260 Mg˙M^-³, µ = 0.350
mm^-¹, T = 298 (2) K. Of the 6010 reflections collected, 1401 were unique (R _int = 0.0326). Refinement on all data converged at R1 = 0.0412, wR2 = 0.1092.