Application of the Lithiation−Borylation Reaction to the Preparation of Enantioenriched Allylic Boron Reagents and Subsequent In Situ Conversion into 1,2,4-Trisubstituted Homoallylic Alcohols with Complete Control over All Elements of Stereochemistry
- Martin Althaus 1
-
Adeem Mahmood
1
-
José Ramón Suárez
1
- Stephen P. Thomas 1
-
Varinder K. Aggarwal
1
- 1 School of Chemistry, University of Bristol, Cantock’s Close, Bristol, BS8 1TS, U.K.
ISSN: 0002-7863, 1520-5126
Año de publicación: 2010
Volumen: 132
Número: 11
Páginas: 4025-4028
Tipo: Artículo
Otras publicaciones en: Journal of the American Chemical Society
Resumen
The reactions of Hoppe’s lithiated carbamates with vinylboranes and boronic esters give allylic boranes/boronic esters, and subsequent addition of aldehydes provides a new route to enantioenriched homoallylic alcohols with high enantiomeric ratios and diastereomeric ratios. Specifically, reactions of sparteine-complexed lithiated carbamates with trans-alkenyl-9-BBN derivatives followed by addition of aldehydes gave (Z)-anti-homoallylic alcohols in greater than 95:5 er and 99:1 dr. However, in the special case of the methyl-substituted lithiated carbamate, diamine-free conditions were required to achieve high selectivity. Reactions of sparteine-complexed lithiated carbamates with (Z)-alkenyl pinacol boronic esters and (E)-alkenyl neopentyl boronic esters gave (E)-syn- and (E)-anti-homoallylic alcohols, respectively, in greater than 96:4 er and 98:2 dr. In these reactions, a Lewis acid (MgBr2 or BF3·OEt2) was required to promote both the 1,2-metalate rearrangement and the addition of the intermediate allylic boronic ester to the aldehyde. This methodology provides a general route to each of the three classes of homoallylic alcohols with high selectivity.
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