A new asymmetric synthesis of cyanohydrins and oxygen-functionalized derivatives: stereoselective addition of cyanide to chiral rhenium aldehyde and ketone complexes of the formula [(.eta.5-C5H5)Re(NO)(PPh3)(O:CRR')]+BF4- Academic Article uri icon

abstract

  • Reactions of racemic and optically active η aldehyde complexes [(η5-C5H5)Re(NO)(PPh3)(η2-O=CHR)]+ BF4− (1; R = a, CH3; b, CH2CH3; c, CH(CH3)2; d, CH2C6H5; e, C6H5) with (CH3CH2)4N+ CN− (CH2Cl2, -80 °C) give cyanohydrin alkoxide complexes (η5-C5H5)Re(NO)(PPh3)(OCH(CN)R) (3a-e, 78-95%) in 89-53% de. Subsequent reactions of (+)-(RS)-3a-e with (-)-(R)-C6H5(CH3O)(F3C)CC(=O)Cl (MTPA-Cl) and DMAP in C6H6 give optically active esters MTPA-OCH(CN)R (96-85%; 90-56% de). Analogous reactions of racemic σ-methyl ketone complexes [(η5-C5H5)Re(NO)(PPh3)(η1-O=C(CH3)R)]+ BF4− (2; R = a, CH3; b, CH2CH3; c, CH(CH3)2; d, C(CH3)3; e, C6H5) and (CH3CH2)4N+ CN− give alkoxide complexes (η5-C5H5)Re(NO))(PPh3)(OCCH3(CN)R) (5a-e, 60-88%) in 71-99% de. A similar reaction of 2e and (CH3)3SiC≡CLi gives (η5-C5H5)Re(NO)(PPh3)(OCCH3(C≡CSi(CH3)3)C6H5) (88%) in 94% de. Mechanisms of diastereoselection are briefly discussed. © 1991, American Chemical Society. All rights reserved.

author list (cited authors)

  • Dalton, D. M., Garner, C. M., Fernandez, J. M., & Gladysz, J. A.

citation count

  • 34

publication date

  • November 1991