Bicyclic methylene aziridines and reactions thereof
AssigneeWisconsin Alumni Research Foundation
InventorsJennifer Schomaker, Luke Boralsky, John Hershberger, Jared Rigoli, Christopher S. Adams
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Abstract
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.
Claims12
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.
A method of forming a bicyclic N,N-aminal, the method comprising:
- combining an allene, a rhodium catalyst, a solvent, and an oxidant, to provide a reaction mixture, thereby initiating an intramolecular allene aziridination reaction, to provide a bicyclic methylene aziridine;
- wherein the allene comprises an allene group tethered to an amino group (—NH2), and the amino group is separated from the nearest carbon atom of the allene group by 3, 4, 5, or 6 atoms linearly;
- contacting the bicyclic methylene aziridine with a nitrene equivalent in the presence of an oxidant to provide an N,N-spiroaminal;
- and
- contacting the N,N-spiroaminal with a nucleophile to provide a bicyclic, ring-opened nucleophile-addition product.
Dependencies are inferred from the claim text.