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. 2014 Dec 31;136(52):17926-9.
doi: 10.1021/ja5104525. Epub 2014 Dec 17.

Endo-selective Pd-catalyzed silyl methyl Heck reaction

Marvin Parasram  1 , Viktor O Iaroshenko, Vladimir Gevorgyan
Affiliations

Endo-selective Pd-catalyzed silyl methyl Heck reaction

Marvin Parasram et al. J Am Chem Soc. .

Abstract

A palladium (Pd)-catalyzed endo-selective Heck reaction of iodomethylsilyl ethers of phenols and aliphatic alkenols has been developed. Mechanistic studies reveal that this silyl methyl Heck reaction operates via a hybrid Pd-radical process and that the silicon atom is crucial for the observed endo selectivity. The obtained allylic silyloxycycles were further oxidized into (Z)-alkenyldiols.

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Figures

Scheme 1
Scheme 1. Intramolecular Alkyl Heck Reaction
Scheme 2
Scheme 2. Hybrid Pd-Radical Catalytic Cycle
Scheme 3
Scheme 3. Synthetic Utility of the Silyl Methyl Heck Reaction
(i) 3 equiv MeLi, Et2O, 0 °C, 1 h. (ii) 1.1 equiv 1,1-Dimethoxycyclohexane, 1.1 equiv BF3OEt2, DCM, −78 °C to rt, 1 h. (iii) 10 equiv 50% H2O2, 12 equiv KHCO3, 2 equiv KF, DMF, 70 °C, 12 h. (iv) 10 mol % Pd(OAc)2, 20 mol % L, 2.2 equiv iPr2NEt, PhMe, 75 °C, 12 h. (v) 10 equiv tBuOOH, 12 equiv KH, 5 equiv TBAF, NMP, rt, 12 h.
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