GaCl₃- and TiCl₄-Catalyzed Insertion of Isocyanides into a C−S Bond of Dithioacetals

Abstract

The insertion reaction of isocyanide into a C-S bond of dithioacetals is catalyzed by GaCl3 or TiCl4 to afford thioimidates containing an alpha-alkylthio group. Balanced thiophilicity of these Lewis acids is critical for efficient catalysis.

Mass spectrometric and theoretical studies on dissociation of the CS bond in the benzenesulfonic acid and benzenesulfinic acid anion series: Homolytic cleavage vs heterolytic cleavage

“…Activation and cleavage of the CAS bond is a critical component in the study of the organosulfur chemistry [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. A case for example is the hydrodesulfurization (HDS) process in the chemical industry.…”

Gallium and Indium Compounds in Homogeneous Catalysis

“…The cyclopropylmethylation reaction of benzylic and allylic chlorides with cyclopropylmethylstannane may be catalyzed by gallium and indium halides (best performed with GaCl 3 and InBr 3 ) to afford various cyclopropane derivatives along with the corresponding terminal alkene products (15). 18 The X-ray determined (XRD) molecular structure of a butenylgallium dichloride species (see inset in 15) comforted the proposed mechanism, thought to proceed via an initial transmetalation between the stannane species and GaCl 3 yielding a butenylgallium complex.…”

Recent applications of gallium and gallium halides as reagents in organic synthesis

“…78 An investigation into the GaCl 3 -10 catalysed insertion reaction of isocyanides into the C-S bonds of dithioacetals has recently been carried out by Chatani et al 79 They found that a variety of different dithioacetals, both aliphatic and aromatic, could be readily converted to the corresponding thioimidates using GaCl 3 catalysis (Scheme 34). Of the latter, electronrich systems (e.g.…”