Lygin Alexander V, de Meijere Armin
Institut für Organische und Biomolekulare Chemie der Georg-August-Universität Göttingen, Germany.
J Org Chem. 2009 Jun 19;74(12):4554-9. doi: 10.1021/jo9004734.
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).
邻位锂代苯基（-杂芳基）异腈与醛和酮反应，根据反应条件和取代模式，可生成异氰醇8（收率36 - 89%，9例）、4H - 3,1 - 苯并恶嗪9（收率45 - 78%，6例），或经过两种重排反应后生成异苯并呋喃-1(3H)-亚胺（亚胺酞嗪）18（收率52 - 75%，4例），或吲哚啉-2-酮19（收率42 - 79%，2例）。而异氰醇8在铜（I）催化下又可转化为9或18（收率66 - 86%，8例）。2与二氧化碳反应，随后用碘捕获锂化中间体并与亲核试剂进行后续反应，可得到4H - 3,1 - 苯并恶嗪-4-酮39 - Nu和异邻苯二甲酸酐40（收率45 - 60%，3例）。
