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Issue 7, 2012
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Reactions of substituted pyridines with electrophilic boranes

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Abstract

The lutidine derivative (2,6-Me2)(4-Bpin)C5H2N when combined with B(C6F5)3 yields a frustrated Lewis pair (FLP) which reacts with H2 to give the salt [(2,6-Me2)(4-Bpin)C5H2NH][HB(C6F5)3] (1). Similarly 2,2′-(C5H2(4,6-Me2)N)2 and (4,4′-(C5H2(4,6-Me2)N)2 were also combined with B(C6F5)3 and exposed to H2 to give [(2,2′-HN(2,6-Me2)C5H2C5H2(4,6-Me2)N][HB(C6F5)3] (2) and [(4,4′-HN(2,6-Me2)C5H2C5H2(2,6-Me2)N] [HB(C6F5)3] (3), respectively. The mono-pyridine-N-oxide 4,4′-N(2,6-Me2)C5H2C5H2(2,6-Me2)NO formed the adduct (4,4′-N(2,6-Me2)C5H2C5H2(2,6-Me2)NO)(B(C6F5)3) (4) which reacts further with B(C6F5)3 and H2 to give [(4,4′-HN(2,6-Me2)C5H2C5H2(2,6-Me2)NO)B(C6F5)3] [HB(C6F5)3] (5). In a related sense, 2-amino-6-CF3-C5H3N reacts with B(C6F5)3 to give (C5H3(6-CF3)NH)(2-NH(B(C6F5)3)) (6). Similarly, the species, 2-amino-quinoline, 8-amino-quinoline and 2-hydroxy-6-methyl-pyridine were reacted with B(C6F5)3 to give the products as (C9H6NH)(2-NHB(C6F5)3) (7), (C9H6N)(8-NH2B(C6F5)3) (8) and (C5H3(6-Me)NH)(2-OB(C6F5)3) (9), respectively; while 2-amino-6-picoline, 2-amino-6-CF3-pyridine, 2-amino-quinoline, 8-amino-quinoline and 2-hydroxy-6-methyl-pyridine react with ClB(C6F5)2 to give the species (C5H3(6-R)NH)(2-NH(ClB(C6F5)2)) (R = Me (10), R = CF3 (11)) (C9H6NH)(2-NH(ClB(C6F5)2)) (12), (C9H6N)(8-NH2ClB(C6F5)2) (13) and (C5H3(6-Me)NH)(2-OClB(C6F5)2) (14), respectively. In a similar manner, 2-amino-6-picoline and 2-amino-quinoline react with B(C6F5)2H to give (C5H3(6-Me)NH)(2-NH(HB(C6F5)2)) (15) and (C9H6NH)(2-NH(HB(C6F5)2)) (16). The corresponding reaction of 8-amino-quinoline yields (C9H6N)(8-NHB(C6F5)2) (17). In a similar fashion, reaction of 2-amino-6-CF3-pyridine resulted in the formation of (18) formulated as (C5H3(6-CF3)N)(2-NH(B(C6F5)2). Finally, treatment of 15 with iPrMgCl gave (C9H6N)(2-NH(B(C6F5)2)) (19). Crystallographic studies of 1, 2, 4, 6, 7, 10, 11, 12 and 15 are reported.

Graphical abstract: Reactions of substituted pyridines with electrophilic boranes

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Publication details

The article was received on 25 Sep 2011, accepted on 08 Nov 2011 and first published on 20 Dec 2011


Article type: Paper
DOI: 10.1039/C1DT11820J
Citation: Dalton Trans., 2012,41, 2131-2139

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    Reactions of substituted pyridines with electrophilic boranes

    C. B. Caputo, S. J. Geier, D. Winkelhaus, N. W. Mitzel, V. N. Vukotic, S. J. Loeb and D. W. Stephan, Dalton Trans., 2012, 41, 2131
    DOI: 10.1039/C1DT11820J

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