Highly diastereoselective and stereodivergent dihydroxylations of acyclic allylic amines: application to the asymmetric synthesis of 3,6-dideoxy-3-amino-L-talose

Kristína Csatayová; Stephen G Davies; James A Lee; Paul M Roberts; Angela J Russell; James E Thomson; David L Wilson

doi:10.1021/ol200717n

Highly diastereoselective and stereodivergent dihydroxylations of acyclic allylic amines: application to the asymmetric synthesis of 3,6-dideoxy-3-amino-L-talose

Org Lett. 2011 May 20;13(10):2606-9. doi: 10.1021/ol200717n. Epub 2011 Apr 13.

Authors

Kristína Csatayová¹, Stephen G Davies, James A Lee, Paul M Roberts, Angela J Russell, James E Thomson, David L Wilson

Affiliation

¹ Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Oxford, UK.

PMID: 21488631
DOI: 10.1021/ol200717n

Abstract

Aminohydroxylation of tert-butyl sorbate [tert-butyl (E,E)-hexa-2,4-dienoate] using enantiopure lithium (R)-N-benzyl-N-(α-methylbenzyl)amide and (-)-camphorsulfonyloxaziridine gives tert-butyl (R,R,R,E)-2-hydroxy-3-[N-benzyl-N-(α-methylbenzyl)amino]hex-4-enoate in >99:1 dr. Subsequent dihydroxylation under Upjohn conditions (OsO(4)/NMO) gives tert-butyl (2R,3R,4S,5S,αR)-2,4,5-trihydroxy-3-[N-benzyl-N-(α-methylbenzyl)amino]hexanoate (in 95:5 dr) while dihydroxylation under Donohoe conditions (OsO(4)/TMEDA) proceeds with antipodal diastereofacial selectivity to give the (R,R,R,R,R)-diastereoisomer (in 95:5 dr). The amino triols resulting from these dihydroxylation reactions are useful for further elaboration, as demonstrated by the asymmetric synthesis of 3,6-dideoxy-3-amino-L-talose.

MeSH terms

Amines / chemistry*
Amino Sugars / chemical synthesis*
Amino Sugars / chemistry
Lithium / chemistry
Molecular Structure
Stereoisomerism

Substances

3,6-dideoxy-3-amino-L-talose
Amines
Amino Sugars
Lithium