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. 2006 May 10;128(18):6044-5.
doi: 10.1021/ja0602501.

Palladium-catalyzed asymmetric ring expansion of allenylcyclobutanols: an asymmetric Wagner-Meerwein shift

Barry M Trost  1 , Jia Xie
Affiliations

Palladium-catalyzed asymmetric ring expansion of allenylcyclobutanols: an asymmetric Wagner-Meerwein shift

Barry M Trost et al. J Am Chem Soc. .

Abstract

In this study, we developed a palladium-catalyzed atom economic asymmetric Wagner-Meerwein shift of allenylcyclobutanol substrates. It is an excellent method for creating functionalized cyclopentanones with an alpha-chiral O-tertiary center by ring expansion of allenylcyclobutanols. This reaction was initiated by hydropalladation and afforded excellent enantioselectivity as well as atom economy. This method provides an efficient route toward the synthesis of natural products such as trans-kumausyne's family, spiro ring systems. In addition, we obtained excellent diastereoselectivity and enantioselectivity at the same time by using 3-monosubstituted allenylcyclobutanol.

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Figures

Figure 1
Figure 1
Trost Ligands.
Scheme 1
Scheme 1
Rationale for Palladium-Catalyzed Ring Expansion
Scheme 2
Scheme 2
Diastereoselectivity of 3-Monosubstituted Cyclobutanol
Scheme 3
Scheme 3
Assignment of the Absolute Configuration
Scheme 4
Scheme 4
Mechanistic Rationale
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References

    1. For review of atom economy see Trost BM. Science. 1991;254:1471.Trost BM. Angew Chem, Int Ed Engl. 1995;34:259.Trost BM. Acc Chem Res. 2002;35:695.

    1. For transition-metal catalysis see Noyori R, Kitamura M, Ohkuma T. Proc Natl Acad Sci USA. 2004;101:5356.Trost BM. Proc Natl Acad Sci USA. 2004;101:5348.Jacobsen EN, Pfaltz A, Yamamoto H, editors. Comprehensive Asymmetric Catalysis. I–III. Spring; Berlin: 2000.

    1. For review Trost BM, Van Vranken DL. Chem Rev. 1996;96:395.Trost BM, Crawley ML. Chem Rev. 2003;103:2921.

    1. For review see Trost BM. Chem Pharm Bull. 2002;50(1):1.

    1. For reviews, see Trost BM. Chem Ear J. 1998;1:2405.Yamamoto Y, Radhakishman U. Chem Soc Rev. 1999;28:199.Khan FA. Chem Rev. 2000;700:3067.Ma S. Chem Rev. 2005;705:2829.

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