127618-65-9Relevant academic research and scientific papers
Selective binding and activation of one aldehyde enantioface by a chiral transition-metal Lewis acid: Synthesis, structure, and reactivity of rhenium aldehyde complexes [(η5-C5H5)Re(NO)(PPh 3)(η2-O=CHR)]+X-
Garner, Charles M.,Méndez, N. Quirós,Kowalczyk, James J.,Fernández, Jésus M.,Emerson, Kenneth,Larsen, Raymond D.,Gladysz
, p. 5146 - 5160 (2007/10/02)
Reaction of dichloromethane complex [(η5-C5H5)Re(NO)(PPh3)(ClCH 2Cl]+X- (2+PF6- or 2+BF4-) and RCH=O (R = (a) CH3, (b) C2H5, (c) n-C3H7, (d) i-C3H7, (e) C6H5, (f) CH2C6H5) gives π-aldehyde complexes (RS,SR)-[(η5-C5H5)Re(NO)(PPh 3)(η2-O=CHR)]+X- ((RS,SR)-3a-f+X-, 98-77%), in which one RCH=O enantioface is bound with high specificity. Crystal structures of (RS,SA)-3b+BF4- and (RS,SR)-3T*PP6- show the RCH=O carbon to be anti to the PPh3 ligand and the RCH=O group to be syn to the NO ligand. Formyl complex (η5-C5H5)Re(NO)(PPh3)(CHO) (5) and (RS,SR)-3a-f+X- react at -80 °C to give [(η5-C5H5)Re(NO)(PPh3)(CO)] +X- and alkoxide complexes (η5-C5H5)Re(NO)(PPh3)(OCH 2R) (6a-f, 95-80%). Reaction of deuterioformyl complex 5-d1 and (RS,SR)-3a-f+X- gives deuterioalkoxide complexes (η5-C5H5)Re(NO)(PPh3)(OCHDR) (6a-f-d1) as 97-92:3-8 mixtures of (RR,SS)/(RS,SR) diastereomers. Analogous reactions starting with optically active 2+X- give optically active aldehyde and alkoxide complexes with retention of configuration at rhenium. The latter react with electrophiles EX (EX = HI, (CH3)3Sil, CH3COI) to give cleavage products EOCH2R and (η5-C5H5)Re(NO)(PPh3)(X), generally with retention at rhenium. When (+)-(RS)-3a-f+BF4- are treated with (+)-(S)-5-d1 and (-)-(R)-5-d1, (+)-6a-f-d1 form as 99-94:1-6 and 91-84:9-16 mixtures of (RR)/(RS) diastereomers, respectively. Hence, enantiomers of the chiral reductant 5-d1 give different stereoselectivities. Reaction of (+)-6a-f-d1 with (-)-(R)-C6H5CH-(OAc)COOH/DCC/4-(dimethylamino)pyridine gives esters C6H5CH(OAc)COOCHDR that are comparable mixtures of (RR)/(RS) diastereomers and carboxylate (+)-(RR)-(η5-C5H5)Re(NO)(PPh 3)(O(C=O)CH(OAc)C6H5) of >99% de.
