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. 2011 Jun 29;133(25):9716-9.
doi: 10.1021/ja2039248. Epub 2011 Jun 7.

Enantioselective construction of all-carbon quaternary centers by branch-selective Pd-catalyzed allyl-allyl cross-coupling

Ping Zhang  1 , Hai Le, Robert E Kyne, James P Morken
Affiliations

Enantioselective construction of all-carbon quaternary centers by branch-selective Pd-catalyzed allyl-allyl cross-coupling

Ping Zhang et al. J Am Chem Soc. .

Abstract

The Pd-catalyzed cross-coupling of racemic tertiary allylic carbonates and allylboronates is described. This reaction generates all-carbon quaternary centers in a highly regioselective and enantioselective fashion. The outcome of these reactions is consistent with a process that proceeds by way of 3,3'-reductive elimination of bis(η(1)-allyl)palladium intermediates. Strategies for distinguishing the product alkenes and application to the synthesis of (+)-α-cuparenone are also described.

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Figures

Figure 1
Figure 1
Substrate Classes for Allylic Substitution.
Scheme 1
Scheme 1
Scheme 2
Scheme 2
(a) PhI, 10 mol % Pd(OAc)2, Bu4NCl, DMF, 80 °C, 16 h. (b) 5 mol % HG2 catalyst, ethyl acrylate, CH2Cl2, 40 °C, 20 h. (c) B2(pin)2, 3 mol % Pt(dba)3, 3.6 mol % 3,5-Ph2-taddol-PPh, THF; then NaOH, H2O2.
Scheme 3
Scheme 3
See this image and copyright information in PMC

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