REACTIONS OF (CO)5MNSI(CH3)3 AND CO WITH ALDEHYDES AND CYCLIC ETHERS - SYNTHESES OF FUNCTIONALIZED PENTACARBONYLMANGANESE ACYLS AND HOMOLOGATED ORGANIC-COMPOUNDS

Reactions of (CO)5MnSi(CH3)3 (1) and CO with aldehydes RCHO and cyclic ethers OCH2(CH2)nCH2 (n = 0-2) give manganese acyls (CO)5MnCOCH(R)OSi(CH3)3 and (CO)5MnCOCH2(CH2) CH2OSi(CH3)3 (n = 0, 6; n= 1, 9; n= 2, 10) in 26-72% and 54-87 % yields, respectively. Experiments conducted in the absence of CO show that these transformations proceed via labile alkyl intermediates (CO)5MnCH(R)-OSi(CH3)3 and (CO)5MnCH2(CH2)nCH2OSi(CH3)3. Reactions of propylene oxide and cyclohexene oxide with 1 and CO give the manganese acyls expected from SN2 ring opening. When the reaction of 1 with aldehydes is conducted in the presence of (CO)5MnH under careful conditions, homologated aldehydes (CH3)3SiOCHRCHO form in 55-78% yields. Reaction of 1 and (CO)5MnH with oxetane gives (CH3)3- SiOCH2CH2CH2CHO (13, 38%) and (CH3)3SiOCHCH2CH2CH2O (14, 59%). Reaction of 9 and 10 with [(CH3CH2)2N]3S+Si(CH3)3F2- yields 7-butyrolactone (84-95%) and -valerolactone (60-85%), respectively. The mechanisms of these transformations, and their utility in organic and organometallic synthesis, are discussed. 1984, American Chemical Society. All rights reserved.

REACTIONS OF (CO)5MNSI(CH3)3 AND CO WITH ALDEHYDES AND CYCLIC ETHERS - SYNTHESES OF FUNCTIONALIZED PENTACARBONYLMANGANESE ACYLS AND HOMOLOGATED ORGANIC-COMPOUNDS Academic Article