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. 2013 Aug 5;52(32):8395-400.
doi: 10.1002/anie.201302538. Epub 2013 Jun 21.

Catalytic Z-selective cross-metathesis with secondary silyl- and benzyl-protected allylic ethers: mechanistic aspects and applications to natural product synthesis

Tyler J Mann  1 , Alexander W H Speed, Richard R Schrock, Amir H Hoveyda
Affiliations

Catalytic Z-selective cross-metathesis with secondary silyl- and benzyl-protected allylic ethers: mechanistic aspects and applications to natural product synthesis

Tyler J Mann et al. Angew Chem Int Ed Engl. .
No abstract available

Keywords: Z olefins; allylic ethers; cross-metathesis; molybdenum; olefin metathesis.

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Figures

Scheme 1
Scheme 1
Z-Allylic alcohols and their derivatives serve as substrates in stereoselective transformations and reside in biologically active molecules. LG = leaving group.
Scheme 2
Scheme 2
Various complexes used in the initial screening shown in Table 1.
Scheme 3
Scheme 3
Different Mo alkylidenes present in solution: their ease of formation and reactivity can influence the final Z:E ratios. Ad = adamantyl; TBS = t-butyl(dimethyl)silyl.
Scheme 4
Scheme 4
An unhindered alkyne can lead to catalyst inhibition, as shown by complete lack of reactivity when allylic silyl ethers 27 and 28 are subjected to the reaction conditions simultaneously.
Scheme 5
Scheme 5
Application of Z-selective CM of allylic ethers to the preparation of falcarindiol (1) and derivatives 2 and 35 (proposed structure), which possess anti-cancer, anti-fungal and immunosuppressive activity.
See this image and copyright information in PMC

References

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    1. For studies regarding isolation and biological activity of falcarindiol, see: Mitsui S, Torii K, Fukui H, Tsujimura K, Maeda A, Nose M, Nagatsu A, Mizukami H, Morita A. J Pharm Exp Therap. 2010;333:954–960.Wyrembek P, Negri R, Kaczor P, Czyzewska M, Appendino G, Mozrzymas JW. J Nat Prod. 2012;75:610–616.For determination of absolute stereochemistry (through Ru-catalyzed ethenolysis of the Z alkene), see: Ratnayake AS, Hemscheidt T. Org Lett. 2002;4:4667–4669.Tamura S, Ohno T, Hattori Y, Murakami N. Tetrahedron Lett. 2010;51:1523–1525.

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