Reactions of substituted pyridines with electrophilic boranes

Caputo CB, Geier SJ, Winkelhaus D, Mitzel NW, Vukotic VN, Loeb SJ, Stephan DW (2012)
Dalton Transactions 41(7): 2131-2139.

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Abstract
The lutidine derivative (2,6-Me(2))(4-Bpin)C(5)H(2)N when combined with B(C(6)F(5))(3) yields a frustrated Lewis pair (FLP) which reacts with H(2) to give the salt [(2,6-Me(2))(4-Bpin)C(5)H(2)NH][HB(C(6)F(5))(3)] (1). Similarly 2,2 '-(C(5)H(2)(4,6-Me(2))N)(2) and (4,4 '-(C(5)H(2)(4,6-Me(2))N)(2) were also combined with B(C(6)F(5))(3) and exposed to H(2) to give [(2,2 '-HN(2,6-Me(2))C(5)H(2)C(5)H(2)(4,6-Me(2))N][HB(C(6)F(5))(3)] (2) and [(4,4 '-HN(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))N] [HB(C(6)F(5))(3)] (3), respectively. The mono-pyridine-N-oxide 4,4 '-N(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))NO formed the adduct (4,4 '-N(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))NO)(B(C(6)F(5))(3)) (4) which reacts further with B(C(6)F(5))(3) and H(2) to give [(4,4 '-HN(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2)) NO)B(C(6)F(5))(3)] [HB(C(6)F(5))(3)] (5). In a related sense, 2-amino-6-CF(3)-C(5)H(3)N reacts with B(C(6)F(5))(3) to give (C(5)H(3)(6-CF(3))NH)(2-NH(B(C(6)F(5))(3))) (6). Similarly, the species, 2-amino-quinoline, 8-amino-quinoline and 2-hydroxy-6-methyl-pyridine were reacted with B(C(6)F(5))(3) to give the products as (C(9)H(6)NH)(2-NHB(C(6)F(5))(3)) (7), (C(9)H(6)N)(8-NH(2)B(C(6)F(5))(3)) (8) and (C(5)H(3)(6-Me)NH)(2-OB(C(6)F(5))(3)) (9), respectively; while 2-amino-6-picoline, 2-amino-6-CF(3)-pyridine, 2-amino-quinoline, 8-amino-quinoline and 2-hydroxy-6-methyl-pyridine react with ClB(C(6)F(5))(2) to give the species (C(5)H(3)(6-R)NH)(2-NH-(ClB(C(6)F(5))(2))) (R = Me (10), R = CF(3) (11)) (C(9)H(6)NH)(2-NH(ClB(C(6)F(5))(2))) (12), (C(9)H(6)N)(8-NH(2)ClB(C(6)F(5))(2)) (13) and (C(5)H(3)(6-Me)NH)(2-OClB(C(6)F(5))(2)) (14), respectively. In a similar manner, 2-amino-6-picoline and 2-amino-quinoline react with B(C(6)F(5))(2)H to give (C(5)H(3)(6-Me)NH)(2-NH(HB(C(6)F(5))(2))) (15) and (C(9)H(6)NH)(2-NH(HB(C(6)F(5))(2))) (16). The corresponding reaction of 8-amino-quinoline yields (C(9)H(6)N)(8-NHB(C(6)F(5))(2)) (17). In a similar fashion, reaction of 2-amino-6-CF3-pyridine resulted in the formation of (18) formulated as (C(5)H(3)(6-CF(3))N)-(2-NH(B(C(6)F(5))(2)). Finally, treatment of 15 with iPrMgCl gave (C(9)H(6)N)(2-NH(B(C(6)F(5))(2))) (19). Crystallographic studies of 1, 2, 4, 6, 7, 10, 11, 12 and 15 are reported.
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Caputo CB, Geier SJ, Winkelhaus D, et al. Reactions of substituted pyridines with electrophilic boranes. Dalton Transactions. 2012;41(7):2131-2139.
Caputo, C. B., Geier, S. J., Winkelhaus, D., Mitzel, N. W., Vukotic, V. N., Loeb, S. J., & Stephan, D. W. (2012). Reactions of substituted pyridines with electrophilic boranes. Dalton Transactions, 41(7), 2131-2139.
Caputo, C. B., Geier, S. J., Winkelhaus, D., Mitzel, N. W., Vukotic, V. N., Loeb, S. J., and Stephan, D. W. (2012). Reactions of substituted pyridines with electrophilic boranes. Dalton Transactions 41, 2131-2139.
Caputo, C.B., et al., 2012. Reactions of substituted pyridines with electrophilic boranes. Dalton Transactions, 41(7), p 2131-2139.
C.B. Caputo, et al., “Reactions of substituted pyridines with electrophilic boranes”, Dalton Transactions, vol. 41, 2012, pp. 2131-2139.
Caputo, C.B., Geier, S.J., Winkelhaus, D., Mitzel, N.W., Vukotic, V.N., Loeb, S.J., Stephan, D.W.: Reactions of substituted pyridines with electrophilic boranes. Dalton Transactions. 41, 2131-2139 (2012).
Caputo, Christopher B., Geier, Stephen J., Winkelhaus, Daniel, Mitzel, Norbert W., Vukotic, V. Nicolas, Loeb, Stephen J., and Stephan, Douglas W. “Reactions of substituted pyridines with electrophilic boranes”. Dalton Transactions 41.7 (2012): 2131-2139.
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