Synthesis and resolution of an asymmetric arsonium cation. Crystal and molecular structures of (R)-Benzyl(methyl)(4-methylphenyl)(naphthalen-1-yl)- arsonium bromide and hexafluorophosphate

Abstract

The (±)-benzyl(methyl)(4-methylphenyl)(naphthalen-1-yl)arsonium cation has been synthesized and subsequently resolved by fractional crystallization of monohydrogen [R-(R*,R*)]-2,3-bis(benzoyloxy)- butanedioate salts. The separated diastereoisomers were converted into the corresponding optically active arsonium bromides by ion-exchange column chromatography. The absolute configuration of the arsonium cation exhibiting a positive rotation at 589 nm (sodium D line) has been established as (R) by single-crystal X-ray analysis of both the bromide and hexafluorophosphate salts. The arsonium bromide with [α]_D + 54.8º(c, 0.62 in CH₂Cl₂) crystallizes in the orthorhombic space group P2₁2₁2₁ (D₂⁴, No.19) with a 22.472(8), b 15.724(7), c 12.585(5) Å and U 4447(3) ų. The corresponding hexafluorophosphate with [α]_D + 19.3º (c, 0.5 in CH₂Cl₂) crystallizes in the same space group with a 23.56(2), b 16.40(1), c 13.12(1) Å and U 5067(6) Å ³. Benzylidene transfer to benzaldehyde from the arsonium ylide derived from either of the arsonium salts produced optically pure (–)-(S)-methyl(4-methylphenyl)(naphthalen-1-yl)arsine, [α]_D - 115.9º (c, 0.593 in CHCl₃), and partly resolved [R-(R*,R*)]-2,3-diphenyloxiran.