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 May 7;136(18):6534-7.
doi: 10.1021/ja500029w. Epub 2014 Feb 24.

A catalytic enantiotopic-group-selective Suzuki reaction for the construction of chiral organoboronates

Chunrui Sun  1 , Bowman Potter, James P Morken
Affiliations

A catalytic enantiotopic-group-selective Suzuki reaction for the construction of chiral organoboronates

Chunrui Sun et al. J Am Chem Soc. .

Abstract

Catalytic enantiotopic-group-selective cross-couplings of achiral geminal bis(pinacolboronates) provide a route for the construction of nonracemic chiral organoboronates. In the presence of a chiral monodentate taddol-derived phosphoramidite ligand, these reactions occur with high levels of asymmetric induction. Mechanistic experiments with chiral (10)B-enriched geminal bis(boronates) suggest that the reaction occurs by a stereochemistry-determining transmetalation that occurs with inversion of configuration at carbon.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1
Figure 1
Figure 1
Substrate scope of the enantioselective Suzuki coupling.
Scheme 2
Scheme 2. A Route for the Synthesis of (R)-Tolterodine with the Enantiotopic-Group-Selective Suzuki Reaction
Scheme 3
Scheme 3
Scheme 4
Scheme 4
See this image and copyright information in PMC

References

    1. Hall D. G.Boronic Acids, 2nd ed.; Wiley-VCH: Weinheim, 2011.

    1. For a review of Rh-catalyzed asymmetric hydroboration, see:

    2. Carroll A.-M.; O’Sullivan T. P.; Guiry P. J. Adv. Synth. Catal. 2005, 347, 609.

    3. For recent examples, see:

    4. Lee Y.; Hoveyda A. H. J. Am. Chem. Soc. 2009, 131, 3160. - PMC - PubMed
    5. Noh D.; Chea H.; Ju J.; Yun J. Angew. Chem., Int. Ed. 2009, 48, 6062. - PubMed
    6. Smith S. M.; Takacs J. M. J. Am. Chem. Soc. 2010, 132, 1740. - PMC - PubMed
    7. Corberán R.; Mszar N. W.; Hoveyda A. H. Angew. Chem., Int. Ed. 2011, 50, 7079. - PubMed
    8. Smith S. M.; Hoang G. L.; Pal R.; Khaled M. O. B.; Pelter L. S.; Zeng X. C.; Takacs J. M. Chem. Commun. 2012, 48, 12180. - PMC - PubMed
    1. For a review of catalytic enantioselective conjugate borylation, see:Calow A. D. J.; Whiting A. Org. Biomol. Chem. 2012, 10, 5485. - PubMed
    1. Ito H.; Ito S.; Sasaki Y.; Matsuura K.; Sawamura M. J. Am. Chem. Soc. 2007, 129, 14856. - PubMed
    2. Guzman-Martinez A.; Hoveyda A. H. J. Am. Chem. Soc. 2010, 132, 10634. - PMC - PubMed
    3. Ito H.; Kunii S.; Sawamura M. Nat. Chem. 2010, 2, 972. - PubMed
    4. Park J. K.; Lackey H. H.; Ondrusek B. A.; McQuade D. T. J. Am. Chem. Soc. 2011, 133, 2410. - PubMed
    1. Lee J. C. H.; Hall D. G. J. Am. Chem. Soc. 2010, 132, 5544. - PubMed
    2. Carosi L.; Hall D. G. Angew. Chem., Int. Ed. 2007, 46, 5913. - PubMed

Publication types