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Issue 6, 2012
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Frustrated Lewis pair olefin addition reactions: P-, N-, C- and H-based nucleophilic additions to an olefin-tethered borane

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Abstract

The electrophilic alkoxyborane, B(C6F5)2(OC(CF3)2CH2CHCH2) 2, was synthesized and the reactivity of the tethered olefinic fragment examined in frustrated Lewis pair (FLP) addition reactions. Treatment of 2 with tBu3P or Me3P afforded B(C6F5)2(OC(CF3)2CH2CHCH2)(PR3) (R = tBu 3, Me 4) with addition of the nucleophile to the internal carbon of the olefinic group. In contrast, reaction of 2 with bulky nitrogen-based nucleophiles, 2,6-lutidine or 2,2,6,6-tetramethylpiperidine, gave B(C6F5)2(OC(CF3)2CH2CHCH2)(NR′) (R′ = C5H3Me2N 5, NHC5H6Me46) where the nucleophile adds to the terminal carbon of the olefinic unit. Treatment with the carbon-based nucleophiles, 1,2,5-trimethylpyrrole, N-tert-butylpyrrole, 1,3-di-tert-butylimidazole-2-ylidene and benzylidene triphenylphosphorane, afforded the zwitterions B(C6F5)2(OC(CF3)2CH2CHCH2)(R′′) (R′′ = C4H2Me2NMe 7, C4H4NtBu 8, ItBu, 1,3-di-tert-butylimidazole-2-ylidene 9, P(CHPh)Ph310) which contained a new C–C bond at the internal carbon of the olefin. In the presence of 1,2,2,6,6-pentamethylpiperidine and a catalytic amount of B(C6F5)3, 2 reacts with H2 to convert to [HPMP][B(C6F5)2(OC(CF3)2CH2CH2CH2)] (PMP = 1,2,2,6,6-pentamethylpiperidine) 11. DFT calculations provide evidence that this latter reaction proceeds by heterolytic cleavage of H2 by B(C6F5)3 and 1,2,2,6,6-pentamethylpiperidine followed by transfer of the hydride from B(C6F5)3 to the internal carbon of the vinyl group of alkoxyborane 2.

Graphical abstract: Frustrated Lewis pair olefin addition reactions: P-, N-, C- and H-based nucleophilic additions to an olefin-tethered borane

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Publication details

The article was received on 02 Mar 2012, accepted on 20 Mar 2012 and first published on 10 Apr 2012


Article type: Edge Article
DOI: 10.1039/C2SC20262J
Citation: Chem. Sci., 2012,3, 2123-2132
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    Frustrated Lewis pair olefin addition reactions: P-, N-, C- and H-based nucleophilic additions to an olefin-tethered borane

    X. Zhao and D. W. Stephan, Chem. Sci., 2012, 3, 2123
    DOI: 10.1039/C2SC20262J

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