Slattery, CN,Ford, A,Eccles, KS,Lawrence, SE,Maguire, AR

2014

March

Synlett

Synthetic and Mechanistic Aspects on the Competition between C-H Insertion and Hydride Transfer in Copper-Mediated Transformations of alpha-Diazo-beta-Keto Sulfones

Validated

WOS: 5 ()

diazocarbonyl copper catalysis bis(oxazoline) C-H insertion hydride transfer 2,3,5-TRISUBSTITUTED TETRAHYDROFURANS CYCLOPENTANE CONSTRUCTION DIAZOCARBONYL COMPOUNDS CARBONYL-COMPOUNDS CYCLIZATION CHEMOSELECTIVITY REACTIVITIES CARBOXYLATES ESTERS

25

591

595

Competition between C-H insertion and hydride transfer is reported for the copper-catalysed reactions of a range of phenyl-substituted -diazo--keto sulfones. Control of chemoselectivity is possible by alteration of the electronic properties of the diazo substrate. The production of enantioenriched cyclopentanones (up to 89% ee), formed via C-H insertion, and alkylidene tetrahydrofurans (up to 43% ee), produced via hydride transfer, is described. The isolation of products derived from hydride transfer provides mechanistic insight into the copper-mediated C-H insertion of -diazocarbonyl compounds.

10.1055/s-0033-1340471