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. 2013 May 8;135(18):6830-3.
doi: 10.1021/ja402916z. Epub 2013 Apr 24.

Enantioselective redox-relay oxidative heck arylations of acyclic alkenyl alcohols using boronic acids

Tian-Sheng Mei  1 , Erik W Werner, Alexander J Burckle, Matthew S Sigman
Affiliations

Enantioselective redox-relay oxidative heck arylations of acyclic alkenyl alcohols using boronic acids

Tian-Sheng Mei et al. J Am Chem Soc. .

Abstract

A general, highly selective asymmetric redox-relay oxidative Heck reaction using achiral or racemic acyclic alkenols and boronic acid derivatives is reported. This reaction delivers remotely functionalized arylated carbonyl products from acyclic alkenol substrates, with excellent enantioselectivity under mild conditions, bearing a range of useful functionality. A preliminary mechanistic investigation suggests that the regioselectivity of the initial migratory insertion is highly dependent on the electronic nature of the boronic acid and more subtle electronic effects of the alkenyl alcohol.

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Figures

Figure 1
Figure 1
a) Enantioselective β-functionalization reactions. b) Enantioselective redox-relay Heck reactions. c) Mechanistic analysis.
Figure 2
Figure 2
Left: Plot of Log of site-selectivity versus Hammett σ-values derived from the scope presented in Table 2. Right: Plot of Log of site-selectivity versus Δδ 13C chemical shift.
Scheme 1
Scheme 1
Mechanistic analysis of stereochemical course.
See this image and copyright information in PMC

References

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