RESUMO
The mechanism of the asymmetric silylation of alcohols with isothiourea catalysts was studied by employing reaction progress kinetic analysis. These reactions were developed by the Wiskur group, and use triphenyl silyl chloride and chiral isothiourea catalysts to silylate the alcohols. While the order of most reaction components was as expected (catalyst, amine base, alcohol), the silyl chloride was determined to be a higher order. This suggested a multistep mechanism between the catalyst and silyl chloride, with the second equivalent of silyl chloride assisting in the formation of the reactive intermediate leading to the rate-determining step. Through the addition of additives and investigating changes in the silyl chloride, an understanding of the catalyst equilibrium emerged for this reaction and provided pathways for further reaction development.
RESUMO
Carbon atom functionalization via generation of carbanions is the cornerstone of carborane chemistry. In this work, we report the synthesis and structural characterization of free ortho-carboranyl [C2B10H11]-, a three-dimensional inorganic analog of the elusive phenyl anion that features a "naked" carbanion center. The first example of a stable, discrete C(H)-deprotonated carborane anion was isolated as a completely separated ion pair with a crown ether-encapsulated potassium cation. An analogous approach led to the isolation and structural characterization of a doubly deprotonated 1,1'-bis(o-carborane) anion [C2B10H10]2 2-, which is the first example of a discrete molecular dicarbanion. These reactive carbanions are key intermediates in carbon vertex chemistry of carborane clusters.
RESUMO
A new pathway of activation of C-H bonds of alkyl- and arylnitriles by a cooperative action of TaCl5 and PPh3 under mild conditions is reported. Coordination of nitriles to the highly Lewis acidic Ta(V) center resulted in an activation of their aliphatic and aromatic C-H bonds, allowing nucleophilic attack and deprotonation by the relatively weak base PPh3. The propensity of Ta(V) to form multiple bonds to nitrogen-containing ligands is an important driving force of the reaction as it led to a sequence of bond rearrangements and the emergence of, in the case of benzonitrile, a zwitterionic enediimido complex of Ta(V) through CâC double bond formation between two activated nitrile fragments. These transformations highlight the special role of the high-valent transition metal halide in substrate activation and distinguish the reactivity of the TaCl5-PPh3 system from both non-metal- and late transition metal-based frustrated Lewis pairs.
RESUMO
We report a new CH3CN activation mode where an imido group is directly formed by deprotonation of the nitrile coordinated to the highly Lewis acidic Ta(V) center. The unexpected deprotonation of TaCl5(CH3CN) by NEt3 resulted in isolation of the triethylammonium vinylimido complex [HNEt3][Ta(NC(CH2)NEt3)Cl5]. The reaction is proposed to proceed through rearrangement of the initial nucleophilic carbanion to the electrophilic azaallene/carbocation intermediate. The use of more sterically hindered (i-Pr)CN and weakly nucleophilic N(i-Pr)2Et resulted in the isolation of a vinylimido group formed upon dimerization of deprotonated nitriles, suggesting deprotonation as the first step of the transformation.