The intramolecular amination of allenes.

  title={The intramolecular amination of allenes.},
  author={George C. Feast and Lee William Page and Jeremy Robertson},
  journal={Chemical communications},
  volume={46 16},
Rhodium-bound nitrenoids are trapped by tethered allenes generating acyloxy-enamines, aminocyclopropanes, and methylene aziridines. The aminocyclopropanes undergo substitution of the acetoxy group by a variety of nucleophiles. 
38 Citations

Gold(I)-catalysed synthesis of cyclic sulfamidates by intramolecular allene hydroamination.

Six-membered cyclic sulfamidates are prepared in high yields by treatment of allenic sulfamates with readily available gold(I) complexes. The reaction enables formation of N-substituted quaternary

Regioselective Functionalization of Enamides at the α-Carbon via Unsymmetrical 2-Amidoallyl Cations.

A new method to functionalize enamides via an intermediacy of unsymmetrical 2-amidoallyl cations is reported, found to undergo addition with various nucleophiles at the less substituted α-carbon to produce highly substituted enamide in high yields with complete control of regioselectivity.

Nucleophilic vinylic substitution in bicyclic methyleneaziridines: SNVπ or SNVσ?

A stereoselective synthesis of the monodeuterated methyleneaziridine shown allowed the stereochemical course of formal SNV-mode ring-opening with copper-based organometallics to be assigned.

Catalytic intermolecular alkene oxyamination with nitrenes.

The Rh(II)-catalyzed intermolecular addition of nitrenes to aromatic and aliphatic alkenes provides vicinal amino alcohols with yields of up to 95 % and complete regioselectivity. This

Structure and reactivity of bicyclic methylene aziridines prepared by intramolecular aziridination of allenes.

Unprecedented bicyclic methylene aziridines are prepared by rhodium(II)-catalyzed alleneAziridination of buta-2,3-dienyl carbamates with preliminary reactivity profile, including overall S(N)V-mode ring-opening with organometallic reagents.

The conversion of allenes to strained three-membered heterocycles.

Methods for converting allenes to strained, three-membered methylene heterocycles, and also covers the reactivity of these products, including applications to the synthesis of complex molecules are described.

Enantioselective Functionalization of Enamides at the β-Carbon Center with Indoles.

We report an enantioconvergent approach for the functionalization of enamides at the β-carbon atom, which involves a chiral Brønsted acid induced tautomerization of 2-amidoallyl into 1-amidoallyl

Rhodium catalyzed allene amidation: a facile entry into 2-amidoallylcations for unusual [3 + 3] annulation reactions

The interaction of a sulfamate ester derived metallonitrene with an allene generates a versatile intermediate with 2-amidoallylcation like reactivity. In this article we outline reactivity patterns



Rhodium catalyzed allene amination: diastereoselective synthesis of aminocyclopropanes via a 2-amidoallylcation intermediate.

The interaction of a sulfamate ester derived metallonitrene with an allene generates a versatile intermediate with 2-amidoallylcation-like reactivity, capable of rearranging to give highly

Copper-catalyzed alkene aziridination with N-tosyloxycarbamates.

Pyridine copper complexes were found as active catalysts for the intramolecular aziridination of allylic N-tosyloxycarbamates and the intermolecularAziridines were easily obtained by basic deprotection of the trichloroethyl group.

The tethered aminohydroxylation (TA) of cyclic allylic carbamates.

The tethered aminohydroxylation of cyclic allylic carbamates is described using catalytic amounts of potassium osmate to form an imido-osmium complex which adds intramolecularly to alkenes with complete control of both regio- and stereoselectivity.

Copper-catalyzed tethered aziridination of unsaturated N-tosyloxy carbamates.

This methodology has been used to demonstrate its utility in the regio- and stereoselective synthesis of a 1,2-diamino-3-hydroxycyclohexane and is found in natural products such as Tamiflu.

A Rh-Catalyzed C-H Insertion Reaction for the Oxidative Conversion of Carbamates to Oxazolidinones.

The reaction is stereospecific, providing access to chiral α-branched amines from optically pure starting materials with no loss in enantiomeric excess.

Rh(II)-catalysed room temperature aziridination of homoallyl-carbamates.

Rhodium(II) catalysts and PhIO in benzene convert homoallylic carbamates into the corresponding aziridines at room temperature.

Cyclisation of azidoformates, formation of aziridines

Thermolysis of azidoformate (1) in refluxing 1,1,2,2-tetrachloroethane gave aziridine (2), while the same azide decomposed in toluene gave the phenoxy carbonyl azepine (6).

Stereochemical models for rh-catalyzed amination reactions of chiral sulfamates.

St stereoselective intramolecular aziridination with substituted homoallyl sulfamates is demonstrated and is rationalized through an analogous stereochemical construct, to support a proposed transition state model that accounts for the observed stereoinduction.