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Volumn 47, Issue 30, 2008, Pages 5600-5604

Regioselective hydroxysulfenylation of α,β-unsaturated imines: Enhanced stability of an intermediate radical

Author keywords

Hydroxysulfenylation; Oxime ethers; Oxygen; Radicals; Thiols

Indexed keywords

CHEMICAL REACTIONS; NITROGEN COMPOUNDS;

EID: 49649111658     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200801041     Document Type: Article
Times cited : (54)

References (49)
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    • b) M. P. Bertrand, C. Ferreri in Radicals in Organic Synthesis, Vol. 2 (Eds.: P. Renaud, M. P. Sibi), Wiley-VCH, Weinheim, 2001, pp. 485-504.
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    • Bertrand, M.P.1    Ferreri, C.2
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    • 33947120199 scopus 로고    scopus 로고
    • For recent reactions with thiyl radicals, see: a
    • For recent reactions with thiyl radicals, see: a) G. K. Friestad, T. Jiang, A. K. Mathies, Org. Lett. 2007, 9, 777;
    • (2007) Org. Lett , vol.9 , pp. 777
    • Friestad, G.K.1    Jiang, T.2    Mathies, A.K.3
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    • 0000457447 scopus 로고
    • For the reaction of carbonyl-stabilized radicals, see: a
    • For the reaction of carbonyl-stabilized radicals, see: a) K. Nozaki, K. Oshima, K. Utimoto, Tetrahedron Lett. 1988, 29, 1041;
    • (1988) Tetrahedron Lett , vol.29 , pp. 1041
    • Nozaki, K.1    Oshima, K.2    Utimoto, K.3
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    • We have explored the generation of N-borylenamine species, see: M. Ueda, H. Miyabe, H. Sugino, O. Miyata, T. Naito, Angew. Chem. 2005, 117, 6346;
    • We have explored the generation of N-borylenamine species, see: M. Ueda, H. Miyabe, H. Sugino, O. Miyata, T. Naito, Angew. Chem. 2005, 117, 6346;
  • 32
    • 2942702314 scopus 로고    scopus 로고
    • For our reviews on radical reactions of imines, see: a
    • For our reviews on radical reactions of imines, see: a) H. Miyabe, M. Ueda, T. Naito, Synlett 2004, 1140;
    • (2004) Synlett , pp. 1140
    • Miyabe, H.1    Ueda, M.2    Naito, T.3
  • 35
    • 0035498332 scopus 로고    scopus 로고
    • -1; for reviews on alkylboranes, see: a) C. Ollivier, P. Renaud, Chem. Rev. 2001, 101, 3415;
    • -1; for reviews on alkylboranes, see: a) C. Ollivier, P. Renaud, Chem. Rev. 2001, 101, 3415;
  • 37
    • 0011568162 scopus 로고    scopus 로고
    • 2; see: H. Gilman, J. F. Nelson, J. Am. Chem. Soc. 1937, 59, 935.
    • 2; see: H. Gilman, J. F. Nelson, J. Am. Chem. Soc. 1937, 59, 935.
  • 38
    • 53549097170 scopus 로고    scopus 로고
    • 1H NMR spectroscopy, see the Supporting Information.
    • 1H NMR spectroscopy, see the Supporting Information.
  • 39
    • 0001172605 scopus 로고    scopus 로고
    • The radical B was also stabilized by a homoconjugative interaction between the p orbital on the trigonal carbon atom and the unoccupied 3d orbitals on the sulfur atom, see: Ref. [2] and P. J. Krusic, J. K. Kochi, J. Am. Chem. Soc. 1971, 93, 846.
    • The radical B was also stabilized by a homoconjugative interaction between the p orbital on the trigonal carbon atom and the unoccupied 3d orbitals on the sulfur atom, see: Ref. [2] and P. J. Krusic, J. K. Kochi, J. Am. Chem. Soc. 1971, 93, 846.
  • 40
    • 53549095297 scopus 로고    scopus 로고
    • All reactions were examined with (E)-oxime ethers.
    • All reactions were examined with (E)-oxime ethers.
  • 41
    • 53549086767 scopus 로고    scopus 로고
    • A competition experiment using 9 and 10 gave the Michael adduct 12 and β-hydroxysulfide 13a, see the Supporting Information.
    • A competition experiment using 9 and 10 gave the Michael adduct 12 and β-hydroxysulfide 13a, see the Supporting Information.
  • 42
    • 53549122829 scopus 로고    scopus 로고
    • The use of 4.0 equivalents of thiophenol gave a small amount of the Michael addition product.
    • The use of 4.0 equivalents of thiophenol gave a small amount of the Michael addition product.
  • 43
    • 53549108145 scopus 로고    scopus 로고
    • 2 acts as a promoter for the reduction of hydroperoxide F, see the Supporting Information.
    • 2 acts as a promoter for the reduction of hydroperoxide F, see the Supporting Information.
  • 46
    • 53549095530 scopus 로고    scopus 로고
    • Triethylborane is an optimal radical initiator, see the Supporting Information
    • Triethylborane is an optimal radical initiator, see the Supporting Information.
  • 47
    • 53549094497 scopus 로고    scopus 로고
    • Determination of the relative configuration of anti-13a, syn-13a, trans-31, cis-31, trans-32, trans-33, trans-34, and the related NOESY experiments are provided in the Supporting Information.
    • Determination of the relative configuration of anti-13a, syn-13a, trans-31, cis-31, trans-32, trans-33, trans-34, and the related NOESY experiments are provided in the Supporting Information.
  • 49
    • 53549094233 scopus 로고    scopus 로고
    • β-Hydroxysulfide 34 was obtained as a 1:1 diastereomeric mixture (with respect to the stereocenter on the side chain).
    • β-Hydroxysulfide 34 was obtained as a 1:1 diastereomeric mixture (with respect to the stereocenter on the side chain).


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