Three Coordinated Organoaluminum Cation for Rapid and Selective Cyanosilylation of Carbonyls under Solvent‐Free Conditions

Abstract

The well-defined three coordinated electronically unsaturated cationic organoaluminum complex [({(2,6-iPr 2 C 6 H 3 N)P(Ph 2 )} 2 N) AlMe] + [MeB(C 6 F 5 ) 3 ] À (1), has been utilized to catalyze the cyanosilylation of aldehydes and ketones under mild and solvent-free conditions. Moreover, catalyst 1 showed high chemoselective cyanosilylation of aldehydes over ketones, nitriles and olefins. The multinuclear NMR investigations revealed that cyanosilylation proceeds via Lewis adduct formation between 1 and TMSCN thereby activating TMSCN (Si-CN bond) followed by nucleophilic attack of the carbonyl oxygen at the Si center of the activated silane and formation of the product.

Waste-Minimized Cyanosilylation of Carbonyls Using Fluoride on Polymeric Ionic Tags in Batch and under Continuous Flow Conditions

“…Therefore, catalytic methods are more commonly applied as they provide better results with mild experimental conditions. Several catalysts have been developed for the cyanosilylation of carbonyls, either under homogeneous − or heterogeneous conditions, − along with methodologies for recovering and reusing homogeneous catalysts. , From the sustainability point of view, easily separable solid catalysts are the preferable choice. The heterogeneous catalysts developed for cyanosilylation reactions may tentatively be classified into three major categories: (i) polyoxometalates, − which mainly act as Lewis bases; (ii) metal–organic frameworks − that exert mainly the role of Lewis acids; and (iii) organocatalysts (e.g., supported phosphine and supported ionic liquid-like phase , ).…”

Isolation of a Nitromethane Anion in the Calix-Shaped Inorganic Cage

“…The turnover frequency reaches 19 min −1 . This value is the highest level among the previous reports [35][36][37][38]. By the addition of V12(NM) into the reaction solution, V12(NM) was easily decomposed due to the formation of electrophilic trimethylsilyl cations and/or the successive formation of nucleophilic cyanide.…”

Structural Similarity in a Series of Alkali Metal Aluminates with Heteroleptic tert‐Butoxide–Isobutyl Ligand Sets

“…The development and fundamental study of well-defined organoaluminium compounds is therefore currently undergoing a resurgence. [8,[16][17][18][19][20][21][22] Our specific interest in this resurgence overlaps with our general interest in alkali-metal-mediated synergistic effects in polar main group organometallic chemistry, the subject of a recent review article. [23] This work has resulted in the synthesis of bimetallic lithium organoaluminate complexes that have PMDETA.…”