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. 2011 Nov 18;76(22):9269-77.
doi: 10.1021/jo201478d. Epub 2011 Oct 25.

Bi(OTf)3-, TfOH-, and TMSOTf-mediated, one-pot epoxide rearrangement, addition, and intramolecular silyl-modified Sakurai (ISMS) cascade toward dihydropyrans: comparison of catalysts and role of Bi(OTf)3

R Frederick Lambert  1 , Robert J Hinkle, Stephen E Ammann, Yajing Lian, Jia Liu, Shane E Lewis, Robert D Pike
Affiliations

Bi(OTf)3-, TfOH-, and TMSOTf-mediated, one-pot epoxide rearrangement, addition, and intramolecular silyl-modified Sakurai (ISMS) cascade toward dihydropyrans: comparison of catalysts and role of Bi(OTf)3

R Frederick Lambert et al. J Org Chem. .

Abstract

Catalytic quantities of bismuth(III) triflate efficiently initiate the rearrangement of epoxides to aldehydes, which subsequently react with (Z)-δ-hydroxyalkenylsilanes to afford 2,6-disubstituted 3,6-dihydro-2H-pyrans. Isolated yields of desired products using Bi(OTf)(3) were compared with yields obtained when the reactions were run with TfOH and TMSOTf in the presence and absence of several additives. These studies, as well as NMR spectroscopic analyses, indicate an initial Lewis acid/base interaction between Bi(OTf)(3) and substrates providing TfOH in situ.

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Figures

Figure 1
Figure 1
Proposed steric hindrance limiting the transformation of trans-Stilbene oxide to the desired DHP Product.
Scheme 1
Scheme 1
Overall mechanism for silyl-Prins reaction affording cis-dihydropyrans.
Scheme 2
Scheme 2
Side-chain exchange reactions of oxocarbenium ion intermediates.
Scheme 3
Scheme 3
In situ generation of ionic triflates by interaction of substrates and Bi(OTf)3.
Scheme 4
Scheme 4
Proposed mechanism for combined rearrangement, addition, and ISMS reaction to dihydropyrans, 3.
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