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

  1. Martin Althaus 1
  2. Adeem Mahmood 1
  3. José Ramón Suárez 1
  4. Stephen P. Thomas 1
  5. Varinder K. Aggarwal 1
  1. 1 School of Chemistry, University of Bristol, Cantock’s Close, Bristol, BS8 1TS, U.K.
Aldizkaria:
Journal of the American Chemical Society

ISSN: 0002-7863,  1520-5126

Argitalpen urtea: 2010

Alea: 132

Zenbakia: 11

Orrialdeak: 4025-4028

Mota: Artikulua

DOI: 10.1021/JA910593W GOOGLE SCHOLAR lock_openSarbide irekia editor

Beste argitalpen batzuk: Journal of the American Chemical Society

Laburpena

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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