Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.
J Am Chem Soc. 2011 Apr 20;133(15):5752-5. doi: 10.1021/ja201035b. Epub 2011 Mar 28.
The mechanisms of the Fischer indole synthesis and competing cleavage pathways were explored with SCS-MP2/6-31G(d) and aqueous solvation calculations. Electron-donating substituents divert the reaction pathway to heterolytic N-N bond cleavage and preclude the acid-promoted [3,3]-sigmatropic rearrangement.
采用 SCS-MP2/6-31G(d) 和水溶剂化计算方法,探索了 Fischer 吲哚合成反应的机理和竞争裂解途径。供电子取代基改变了反应途径,有利于异裂 N-N 键断裂,并且阻止了酸促进的[3,3]-σ重排。