Reactions of ortho-lithiophenyl (-hetaryl) isocyanides with carbonyl compounds: rearrangements of 2-metalated 4H-3,1-benzoxazines.
ortho-Lithiophenyl (-hetaryl) isocyanides react with aldehydes and ketones providing isocyanoalcohols 8 (36-89%, nine examples), 4H-3,1-benzoxazines 9 (45-78%, six examples) or, after two types of rearrangements, isobenzofuran-1(3H)-imines (iminophthalanes) 18 (52-75%, four examples), or indolin-2-ones 19 (42-79%, two examples), depending on the reaction conditions and substitution patterns. Isocyanoalcohols 8, in turn, were converted to 9 or 18 under Cu(I) catalysis (66-86%, eight examples). 4H-3,1-Benzoxazin-4-ones 39-Nu and isatoic anhydride 40 were obtained by the reaction of 2 with carbon dioxide followed by trapping of the lithiated intermediate with iodine and subsequent reactions with nucleophiles (45-60%, three examples).
Lygin
Alexander V
AV
Institut für Organische und Biomolekulare Chemie der Georg-August-Universität Göttingen, Germany.
de Meijere
Armin
A
D000447:Aldehydes / Q000737:chemistry*; D001572:Benzofurans / Q000138:chemical synthesis / Q000737:chemistry; D048588:Benzoxazines / Q000138:chemical synthesis / Q000737:chemistry*; D001592:Benzyl Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D003486:Cyanides / Q000737:chemistry*; D007097:Imines / Q000138:chemical synthesis / Q000737:chemistry; D007211:Indoles / Q000138:chemical synthesis / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*
D000447:Aldehydes; D001572:Benzofurans; D048588:Benzoxazines; D001592:Benzyl Alcohols; D003486:Cyanides; D007097:Imines; D007211:Indoles; C503753:Indolinone A; D007659:Ketones; D009942:Organometallic Compounds; D008094:Lithium