Novel uses of amino carbinols and amino alkoxides as intermediates in synthesis

ORGN 60

Darren J. Dixon and Amanda C. Lucas. Department of Chemistry, University of Cambridge, Lensfield Rd, Cambridge, CB2 1EW, United Kingdom
Amino alkoxides are known to be short lived intermediates in acyl transfer reactions. At the other extreme in anionic formylation reactions, where the formyl source is an N-formylated amine, the intermediate amino alkoxide is stable until dilute acidic work-up when the intermediate collapses and the aldehyde is released.

We have identified that the amino alkoxide formed upon addition of an organometallic reagent to N-formyl carbazole is metastable, allowing the development of a one-pot carbanion formylation/trapping sequence. We describe the application of this procedure to the synthesis of α,β-unsaturated esters and unsymmetric secondary carbinols.

Additionally, where the amino alkoxide can be trapped as the N-carbinol, work is underway to use the asymmetric carbinol, formed by Felkin-Anh addition of nitrogen heterocycle to chiral aldehyde, as a novel stereodirecting element. Studies towards indole alkaloid synthesis using this methodology will be described.

 

New Reactions and Methodology, Metal-Mediated Reactions, Heterocycles and Aromatics
8:00 PM-10:00 PM, Sunday, March 28, 2004 Anaheim Convention Center -- Hall A, Poster

Division of Organic Chemistry

The 227th ACS National Meeting, Anaheim, CA, March 28-April 1, 2004