Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 24, Issue 48, Pages 12669-12677Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201801909
Keywords
density functional calculations; epoxides; frustrated Lewis pairs; kinetic studies; ring-opening reactions
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Funding
- European Union (Marie Curie ITN SusPhos) [317404]
- Council for Chemical Sciences of The Netherlands Organization for Scientific Research (NWO/CW) by a VIDI grant
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Treatment of the preorganized frustrated Lewis pairs (FLPs) tBu(2)PCH(2)BPh(2) (1) and o-Ph2P(C6H4)BCat (Cat=catechol) (4) with 2-methyloxirane, 2-phenyloxirane and 2-(trifluoromethyl)oxirane resulted in epoxide ring-opening to yield the six- and seven-membered heterocycles 2a-c and 5a-c, respectively. These zwitterionic products were characterized spectroscopically, and compounds 2a, 2b, 5a and 5c were structurally characterized by single-crystal X-ray structure analyses. Based on computational and kinetic studies, the mechanism of these reactions was found to proceed via activation of the epoxide by the Lewis acidic borane moiety followed by nucleophilic attack of the phosphine of a second FLP molecule. The resulting chain-like intermediates afford the final cyclic products by ring-closure and concurrent release of the second equivalent of FLP that behaves as catalyst in this reaction.
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