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Instead of reductive elimination of aldehyde, or decarbonylation to give a trifluoroalkyl hydride, heating Cp*(PMe3)Ir(H)[C(O)CF3] (1) leads to the quantitative formation of Cp*(PMe3)Ir(CO) (2) and CF3H. Kinetic experiments, isotope labeling studies, solvent effect studies, and solvent-inclusive DFT calculations support a mechanism that involves initial dissociation of trifluoromethyl anion to give the transient ion-pair intermediate [Cp*(PMe3)Ir(H)(CO)]+[CF3]-. Further evidence for the ability of CF-3 to act as a leaving group came from the investigation of the analogous methyl and chloride derivatives Cp*(PMe3)Ir(Me)[C(O)CF3] and Cp*(PMe3)Ir(Cl)[C(O)CF3]. Both of these compounds undergo a similar loss of trifluoromethyl anion, generating an iridium carbonyl cation and CF3D in CD3OD. Three additional acyl hydrides, Cp*(PMe3)Ir(H)[C(O)RF] (where RF = CF2CF3, CF2CF2CF3, or CF2(CF2)6CF3) undergo RF--H elimination to give 2 at a faster rate than CF3H elimination from 1. Stereochemical studies using a chiral acyl hydride with a stereocenter at the β-position reveal that ionization of the carbanion occurs to form a tight ion-pair with high retention of configuration and enantiomeric purity upon proton transfer from iridium. [ABSTRACT FROM AUTHOR]

This article describes an efficient synthesis of a potent trehalase inhibitor, 1,1'-N-linked pseudodisaccharide 1 (consisting of two valienamines), in 14 steps with an overall yield of 12% and a first synthesis of 2 (consisting of two 2-epi-valienamines) in 15 steps with an overall yield of 24% from (-)-quinic acid. The synthesis involves a stereospecific palladium-catalyzed coupling reaction between an allylic amine and an allylic chloride as the crucial step. The acetonide blodking groups were shown to be the best hydroxyl protecting groups, compatible with the palladium-catalyzed allylic amination reaction that afforded high yields of the 1,1'-N-linked pseudodisaccharicles with a minimum amount of an elimination diene side product. [ABSTRACT FROM AUTHOR]