Reactions of InMe3 with isocyanides in the presence of amines: chemical and mass spectrometric evidence of unprecedented insertion into InN bonds

Coordination Chemistry of Main Group Metals with Organic Isocyanides

“…Insertion of isocyanides across In−N bond from an isocyanide coordinated Indium complexes 104 a and 104 b observed when the Me 3 InCNR (R= p ‐MeO−C 6 H 4 , p ‐Me−C 6 H 4 ) complex is reacted with pyrrolidine [55b] . The same products were also obtained directly when the pyrrolidine coordinated dimethyl indium complex reacted with isocyanides, as displayed in Scheme 44.…”

Direct Alkylative Passerini Reaction of Aldehydes, Isocyanides, and Free Aliphatic Alcohols Catalyzed by Indium(III) Triflate

“…In the absence of tert -butyl isocyanide, the reaction of benzaldehyde 1a in 2-propanol in the presence of 20 mol % of In(OTf) 3 gave benzyl alcohol in 95% yield, which was possibly generated by In(OTf) 3 -catalyzed Meerwein−Ponndorf−Verley (MPV) reduction through the simultaneous coordination of both carbonyl oxygen of benzaldehyde and hydroxy oxygen of 2-propanol to the In(III) center (eq 1) . This finding indicated that further addition of isocyanide completely retards the MPV reduction, possibly via coordination of isocyanide to In complex . Furthermore, the reaction of benzaldehyde dimethyl acetal 1a′ with tert -butyl isocyanide in the presence of In(OTf) 3 in 2-propanol provided the clean formation of α-isopropoxy amide 2a in 69% yield (eq 2).…”

First Practical Synthesis of Formamidine Ureas and Derivatives.

“…Prominent among these is mediation by electrophilic "soft" metals such as Cu, Hg, and Ag, [1][2][3][4][5][6][7][8][9][10] and more recently In. 11 This general scheme has also been applied to hydrazide and sulfonamide nucleophiles. 12,13 A very early report describes the simple addition of amines to isonitriles in the presence of carboxylic acids.…”

“…1-Cyclopropanecarbonyl-1,3-dimethyl-urea(11). Colorless oil:1 H NMR (CD 3 OD) d 1.03-1.07 (m, 4H), 2.18-2.20 (m, 1H), 2.89 (s, 3H), 3.48 (s, 3H); 13 C NMR (CD 3 OD) d 9.0, 14.1, 26.3, 31.4, 156.7, 177.8; IR (CaF 2 , cm -1 ) 3296, 2951, 1720, 1650; MS m/z (relative intensity) 179 (M+Na) + (16), 158 (M+2) + (9), 158 (M+1) + (100), 105 (2).…”