Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2014 Dec 31;136(52):17918-21.
doi: 10.1021/ja510266x. Epub 2014 Dec 15.

Nonracemic allylic boronates through enantiotopic-group-selective cross-coupling of geminal bis(boronates) and vinyl halides

Bowman Potter  1 , Adam A Szymaniak, Emma K Edelstein, James P Morken
Affiliations

Nonracemic allylic boronates through enantiotopic-group-selective cross-coupling of geminal bis(boronates) and vinyl halides

Bowman Potter et al. J Am Chem Soc. .

Abstract

Under the influence of a chiral palladium catalyst, 1,1-bis(pinacolboronate) esters undergo asymmetric cross-coupling with bromoalkenes to generate nonracemic allyl boronates with high levels of enantioselectivity. The so-formed allyl boronates may be oxidized with hydrogen peroxide to provide secondary allylic alcohols or with nitrosobenzene to furnish nonracemic tertiary allylic alcohols. Mechanistic experiments suggest the operation of a pathway involving outer-sphere stereoinvertive transmetalation.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1. Catalytic Enantioselective Routes to γ,γ-Disubstituted Allyl Boronates
Figure 1
Figure 1
Crystal structure of L6·PdCl2. The structure was obtained from a crystal of the racemic complex in the presence of CH2Cl2. Coordinates have been deposited at the Cambridge Crystallographic Data Centre under CCDC 1035172.
Scheme 2
Scheme 2. Tandem Enantioselective Cross-Coupling/Functionalization Cascades
Scheme 3
Scheme 3. Gram-Scale Enantioselective Cross-Coupling To Furnish Allyl Boronate 3
Scheme 4
Scheme 4. Analysis of the Stereochemistry of Transmetalation in Cross-Couplings with L6·PdCl2
See this image and copyright information in PMC

References

    1. For an overview of allylic borylation reactions, see:Lachance H.; Hall D. G. Org. React. 2008, 73, 1.
    1. Kliman L. T.; Mlynarski N.; Ferris G. E.; Morken J. P. Angew. Chem., Int. Ed. 2012, 51, 521. - PMC - PubMed
    1. Ito H.; Kunii S.; Sawamura M. Nat. Chem. 2010, 2, 972. - PubMed

    1. For catalytic enantioselective allylic borylation reactions that do not apply to the construction of γ,γ-disubstituted allyl boronates, see:

    2. Ito H.; Ito S.; Sasaki Y.; Matsuura K.; Sawamura M. J. Am. Chem. Soc. 2007, 129, 14856. - PubMed
    3. Guzman-Martinez A.; Hoveyda A. H. J. Am. Chem. Soc. 2010, 132, 10634. - PMC - PubMed
    4. Park J. K.; Lackey H. H.; Ondrusek B. A.; McQuade D. T. J. Am. Chem. Soc. 2011, 133, 2410. - PubMed
    1. Chen J. L.-Y.; Aggarwal V. K. Angew. Chem., Int. Ed. 2014, 53, 10992. - PubMed

Publication types

LinkOut - more resources