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. 2016 Dec 14;138(49):15877-15880.
doi: 10.1021/jacs.6b11367. Epub 2016 Nov 30.

Development and Analysis of a Pd(0)-Catalyzed Enantioselective 1,1-Diarylation of Acrylates Enabled by Chiral Anion Phase Transfer

Eiji Yamamoto  1 , Margaret J Hilton  1 , Manuel Orlandi  1 , Vaneet Saini  1 , F Dean Toste  2 , Matthew S Sigman  1
Affiliations

Development and Analysis of a Pd(0)-Catalyzed Enantioselective 1,1-Diarylation of Acrylates Enabled by Chiral Anion Phase Transfer

Eiji Yamamoto et al. J Am Chem Soc. .

Abstract

Enantioselective 1,1-diarylation of terminal alkenes enabled by the combination of Pd catalysis with a chiral anion phase transfer (CAPT) strategy is reported herein. The reaction of substituted benzyl acrylates with aryldiazonium salts and arylboronic acids gave the corresponding 3,3-diarylpropanoates in moderate to good yields with high enantioselectivies (up to 98:2 er). Substituents on the benzyl acrylate and CAPT catalyst significantly affect the enantioselectivity, and multidimensional parametrization identified correlations suggesting structural origins for the high stereocontrol.

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Figures

Figure 1
Figure 1
Multidimensional Correlation of Chiral Anion Parameters with Enantioselectivity.
Figure 2
Figure 2
Evaluation and Correlation of Benzyl Acrylate Substituent Effects on Enantioselectivity.
Scheme 1
Scheme 1
Relevance and overview of the enantioselective 1,1-difunctionalization of alkenes
See this image and copyright information in PMC

References

    1. For reviews, see: Jensen KH, Sigman MS. Org. Biomol. Chem. 2008;6:4083. McDonald RI, Liu G, Stahl SS. Chem. Rev. 2011;111:2981.

    1. For recent reviews, see: Ameen D, Snape TJ. Med. Chem. Commun. 2013;4:893. For examples, see: Alexander RP, Warrellow GJ, Eaton MAW, Boyd EC, Head JC, Porter JR, Brown JA, Reuberson JT, Hutchinson B, Turner P, Boyce B, Barnes D, Mason B, Cannell A, Taylor RJ, Zomaya A, Millican A, Leonard J, Morphy R, Wales M, Perry M, Allen RA, Gozzard N, Hughes B, Higgs G. Bioorganic Med. Chem. Lett. 2002;12:1451. Ohlstein EH, Nambi P, Douglas SA, Edwards RM, Gellai M, Lago A, Leber JD, Cousins RD, Gao A, Frazee JS, Peishoff CE, Bean JW, Eggleston DS, Elshourbagy NA, Kumar C, Lee JA, Yue T-L, Louden C, Brooks DP, Weinstock J, Feuerstein G, Poste G, Ruffolo RR, Gleason JG, Elliott JD. Proc. Natl. Acad. Sci. U. S. A. 1994;91:8052. Hyttel J, Larsen JJ. J. Neurochem. 1985;44:1615.

    1. Gligorich K, Vaden R, Shelton D, Wang G, Matsen C, Looper R, Sigman M, Welm B. Breast Cancer Res. 2013;15:R58. - PMC - PubMed
    1. Liao L, Jana R, Urkalan KB, Sigman MS. J. Am. Chem. Soc. 2011;133:5784. - PMC - PubMed
    2. Saini V, Sigman MS. J. Am. Chem. Soc. 2012;134:11372. - PMC - PubMed
    3. Saini V, Liao L, Wang Q, Jana R, Sigman MS. Org. Lett. 2013;15:5008. - PMC - PubMed

    1. Nelson HM, Williams BD, Miró J, Toste FD. J. Am. Chem. Soc. 2015;137:3213. For reviews on chiral ion pairs used in catalysis, see: Phipps RJ, Hamilton GL, Toste FD. Nature Chem. 2012;4:603. Brak K, Jacobsen EN. Angew. Chem. Int. Ed. 2013;52:534.

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