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Volumn 74, Issue 17, 2009, Pages 6735-6748

Ammonium-directed oxidation of cyclic allylic and homoallylic amines

Author keywords

[No Author keywords available]

Indexed keywords

8-MEMBERED RING; CHEMICAL EQUATIONS; DIASTEREO-SELECTIVITY; DIRECTED OXIDATION; FUNCTIONALIZATIONS; HOMOALLYLIC AMINES; OXIDATION REACTIONS; SYNTHETIC INTERMEDIATES;

EID: 69549117003     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9012783     Document Type: Article
Times cited : (61)

References (76)
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    • For a review on substrate-directed reactions, see
    • For a review on substrate-directed reactions, see: Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Chem. Rev. 1993, 93, 1307.
    • (1993) Chem. Rev. , vol.93 , pp. 1307
    • Hoveyda, A.H.1    Evans, D.A.2    Fu, G.C.3
  • 9
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    • For a discussion of the stereochemistry of epoxidation in some homoallylic cyclohexene alcohols, see
    • For a discussion of the stereochemistry of epoxidation in some homoallylic cyclohexene alcohols, see: Kočovský, P. J. Chem. Soc., Perkin Trans. 1 1994, 1759.
    • (1994) J. Chem. Soc., Perkin Trans. 1 , pp. 1759
    • Kočovský, P.1
  • 10
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    • For examples concerning the oxidative functionalization of homoallylic substrates, see ref 1 and
    • For examples concerning the oxidative functionalization of homoallylic substrates, see ref 1 and: Garside, P.; Halsall, T. G.; Hornby, G. M. J. Chem. Soc. C 1969, 716.
    • (1969) J. Chem. Soc. C , pp. 716
    • Garside, P.1    Halsall, T.G.2    Hornby, G.M.3
  • 33
    • 0037111592 scopus 로고    scopus 로고
    • Several instances of syn-selective osmylation and epoxidation reactions of 3-substituted cyclopentenes which proceed in the absence of any obvious associative interactions (e.g., hydrogen bonding) in the transition state have been reported; see: (a)
    • Several instances of syn-selective osmylation and epoxidation reactions of 3-substituted cyclopentenes which proceed in the absence of any obvious associative interactions (e.g., hydrogen bonding) in the transition state have been reported; see: (a) Donohoe, T. J.; Blades, K.; Moore, P. R.; Waring, M. J.; Winter, J. J. G.; Helliwell, M.; Newcombe, N. J.; Stemp, G. J. Org. Chem. 2002, 67, 7946.
    • (2002) J. Org. Chem. , vol.67 , pp. 7946
    • Donohoe, T.J.1    Blades, K.2    Moore, P.R.3    Waring, M.J.4    Winter, J.J.G.5    Helliwell, M.6    Newcombe, N.J.7    Stemp, G.8
  • 36
    • 0024802464 scopus 로고
    • Poli has proposed a model to account for these observations, in which attack on the syn-face is favoured due to minimization of torsional strain in the transition state; see
    • Poli has proposed a model to account for these observations, in which attack on the syn-face is favoured due to minimization of torsional strain in the transition state; see: Poli, G. Tetrahedron Lett. 1989, 30, 7385.
    • (1989) Tetrahedron Lett. , vol.30 , pp. 7385
    • Poli, G.1
  • 37
    • 33646463586 scopus 로고    scopus 로고
    • Houk has coined the term "torsional steering" for this effect; see
    • Houk has coined the term "torsional steering" for this effect; see: Cheong, P. H.-Y.; Yun, H.; Danishefsky, S. J.; Houk, K. N. Org. Lett. 2006, 8, 1513.
    • (2006) Org. Lett. , vol.8 , pp. 1513
    • Cheong, P.H.-Y.1    Yun, H.2    Danishefsky, S.J.3    Houk, K.N.4
  • 40
    • 69549144421 scopus 로고    scopus 로고
    • note
    • H 4.94 (dd, J 7.7, 4.2), 4.97-5.03 (m), 5.29 (dd, J 6.2, 2.9)]. Purification of the crude reaction mixture gave 22 in 83% yield and >99:1 dr, while transesterification of the crude reaction mixture gave an 89:11 mixture of 24:35.
  • 41
    • 69549152418 scopus 로고    scopus 로고
    • note
    • 4 giving crystals of suitable quality for X-ray analysis.
  • 45
    • 1542532787 scopus 로고
    • For a discussion of the conformation of cyclooctane derivatives such as cis-cyclooctene, see
    • For a discussion of the conformation of cyclooctane derivatives such as cis-cyclooctene, see: Still, W. C.; Galynker, I. Tetrahedron 1981, 37, 3981.
    • (1981) Tetrahedron , vol.37 , pp. 3981
    • Still, W.C.1    Galynker, I.2
  • 51
    • 57649180499 scopus 로고    scopus 로고
    • 2- (followed by hydrolysis) may occur. For a very recent example, see
    • 2- (followed by hydrolysis) may occur. For a very recent example, see: Cavdar, H.; Saracoglu, N. Tetrahedron 2009, 65, 985.
    • (2009) Tetrahedron , vol.65 , pp. 985
    • Cavdar, H.1    Saracoglu, N.2
  • 54
    • 69549145255 scopus 로고    scopus 로고
    • note
    • The regiochemistry within 36 and 37 was arbitrarily assigned.
  • 55
    • 69549099482 scopus 로고    scopus 로고
    • note
    • 3). (Chemical Equation Presented)
  • 56
    • 69549147280 scopus 로고    scopus 로고
    • note
    • A range of Brønsted acids were screened for their ability to promote crystallization of 39 as the corresponding ammonium salt, with 2-methyl-5- nitrobenzenesulfonic acid giving crystals of suitable quality for X-ray analysis.
  • 57
    • 69549153941 scopus 로고    scopus 로고
    • note
    • The regiochemistry within 45 and 46 was arbitrarily assigned.
  • 59
    • 69549151509 scopus 로고    scopus 로고
    • note
    • 2H gave 53 as the major product (>95%) along with trace amounts of unidentifiable species. Recrystallization of the crude reaction mixture gave 53 in 87% yield and >99:1 dr, while transesterification gave 54 in >95:5 dr.
  • 60
    • 69549142139 scopus 로고    scopus 로고
    • note
    • The regiochemistry within 56 and 57 was arbitrarily assigned.
  • 61
    • 69549132903 scopus 로고    scopus 로고
    • note
    • 3). (Chemical Equation Presented)
  • 65
    • 69549098641 scopus 로고    scopus 로고
    • note
    • Direct formation of N,N-dibenzyl-protected amine 65 from bromide 63 via displacement with dibenzylamine was not as efficacious.
  • 66
    • 69549148874 scopus 로고    scopus 로고
    • note
    • 1HNMR "titration experiment" as described for allylic amines 14-16.
  • 68
    • 0003294908 scopus 로고    scopus 로고
    • A "strong" hydrogen bond is observed between C(2)O-H. . .N, and a "weak" hydrogen bond is observed between C(1)O-H. . .O-C(2); see: Desiraju, G. R., Steiner, T., Eds.; Oxford University Press: Oxford
    • A "strong" hydrogen bond is observed between C(2)O-H. . .N, and a "weak" hydrogen bond is observed between C(1)O-H. . .O-C(2); see: Desiraju, G. R. The Weak Hydrogen Bond in Structural Chemistry and Biology; Desiraju, G. R., Steiner, T., Eds.; Oxford University Press: Oxford, 1999; p 13.
    • (1999) The Weak Hydrogen Bond in Structural Chemistry and Biology , pp. 13
    • Desiraju, G.R.1
  • 69
    • 69549148072 scopus 로고    scopus 로고
    • note
    • 2,3 4.6); in addition, it is notable that both OH protons are observable, appearing as broad singlets at δH 2.55 and 6.75.
  • 70
    • 69549093882 scopus 로고    scopus 로고
    • note
    • The stereo- and regiochemistries within 77 and 78 were subsequently established by comparison with authentic samples prepared via ring-opening of syn- and anti-epoxides 79 and 80, respectively.
  • 72
    • 69549149935 scopus 로고    scopus 로고
    • note
    • Hydrogen-bonded delivery of the conjugate base to C(2) by the protonated N,N-dibenzylaminomethyl group may also be important in determining the regioselectivity of the ring-opening reaction.
  • 73
    • 69549142137 scopus 로고    scopus 로고
    • note
    • The regiochemistry within 86 and 87 was arbitrarily assigned.
  • 74
    • 69549153030 scopus 로고    scopus 로고
    • note
    • 2, -78 °C, 2 h, then MeOH, HCl, rt, 24 h). (Chemical Equation Presented)
  • 75
    • 69549152417 scopus 로고    scopus 로고
    • note
    • The regiochemistry within 90 and 91 was arbitrarily assigned.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.