| 摘要 |
The oxidative functionalization of olefins is a common method for the formation of vicinal carbon-heteroatom bonds. However, oxidative methods to transform allenes into synthetic motifs containing three contiguous carbon-heteroatom bonds are much less developed. The use of bicyclic methylene aziridines (MAs), prepared via intramolecular allene aziridination, as scaffolds for functionalization of all three allene carbons, among other reactions, is described herein. |
| 主权项 |
1. A method of forming a bicyclic methylene aziridine by an intramolecular allene aziridination reaction, the method comprising:
combining an allene of Formula I:wherein
R1, R2, and R3 are each independently H, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, (alkyl)cycloalkyl, (alkyl)aryl, (alkyl)heteroaryl, or (alkyl)heterocycle; n is 1, 2, or 3; Y is —C(═O)— or —S(═O)2—; and each Z is independently —(CH2)—, —(CHR1), or —(C(R1)2)—; a rhodium catalyst selected from the group consisting of Rh2(esp)2 where esp is α,α,α′,α′-tetramethyl-1,3-benzenedipropionate, and Rh2(TPA)4 where TPA is triphenylacetate; a solvent; and an oxidant; to yield a reaction mixture, thereby initiating an intramolecular allene aziridination reaction, to provide a bicyclic methylene aziridine; and contacting the bicyclic methylene aziridine with a nucleophile to provide a nucleophile-addition product. |
