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Volumn 11, Issue 11, 2009, Pages 2437-2440

Anti-selective epoxidation of methyl α-methylene-β-tert- butyldimethylsilyloxycarboxylate esters. evidence for stereospecific oxygen atom transfer in a nucleophilic epoxidation Process

Author keywords

[No Author keywords available]

Indexed keywords

EPOXIDE; ESTER; ORGANOSILICON DERIVATIVE;

EID: 66149162962     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol900665a     Document Type: Article
Times cited : (24)

References (28)
  • 3
    • 0034640883 scopus 로고    scopus 로고
    • To the best of our knowledge, these conditions were first reported in the following works: (a) Warrener, R. N.; Butler, D. N.; Margetic, D.; Pfeffer, F. M.; Russell, R. A. Tetrahedron Lett. 2000, 41, 4671-4675.
    • To the best of our knowledge, these conditions were first reported in the following works: (a) Warrener, R. N.; Butler, D. N.; Margetic, D.; Pfeffer, F. M.; Russell, R. A. Tetrahedron Lett. 2000, 41, 4671-4675.
  • 4
    • 0037039032 scopus 로고    scopus 로고
    • Pfeffer, F. M.; Russell, R. A. J. Chem. Soc., Perkin Trans. 1 2002, 2680- 2685. Although we have successfully used anhydrous solid potassium tertbutoxide in several experiments, for convenience we typically employ a 1.0 M stock solution of base in THF, prepared from the anhydrous solid (see the Supporting Information).
    • Pfeffer, F. M.; Russell, R. A. J. Chem. Soc., Perkin Trans. 1 2002, 2680- 2685. Although we have successfully used anhydrous solid potassium tertbutoxide in several experiments, for convenience we typically employ a 1.0 M stock solution of base in THF, prepared from the anhydrous solid (see the Supporting Information).
  • 6
    • 0030909214 scopus 로고    scopus 로고
    • m-CPBA: Singleton, D. A.; Merrigan, S. R.; Liu, J.; Houk, K. N. J. Am. Chem. Soc. 1997, 119, 3385-3386, and references therein. Dimethyldioxirane: (a) Adam,W.; Curci, R.; Edwards, J. O. Acc. Chem. Res. 1989, 22, 205-211.
    • m-CPBA: Singleton, D. A.; Merrigan, S. R.; Liu, J.; Houk, K. N. J. Am. Chem. Soc. 1997, 119, 3385-3386, and references therein. Dimethyldioxirane: (a) Adam,W.; Curci, R.; Edwards, J. O. Acc. Chem. Res. 1989, 22, 205-211.
  • 19
    • 66149188167 scopus 로고    scopus 로고
    • Metal-halogen exchange using i-PrMgCl and n-BuLi provided the following isolated yields of labeled substrates
    • Metal-halogen exchange using i-PrMgCl and n-BuLi provided the following isolated yields of labeled substrates
  • 20
    • 66149185335 scopus 로고    scopus 로고
    • : 13 (88% and 85%), 14 (77% and 52%), 15 (87% and 45%), and 16 (91% and 18%).
    • : 13 (88% and 85%), 14 (77% and 52%), 15 (87% and 45%), and 16 (91% and 18%).
  • 21
    • 0001367039 scopus 로고    scopus 로고
    • In the course of developing a synthetic route to the deuteriumlabeled substrates, we made the following observation: treatment of 3-deuteriopropiolate with diisobutylaluminum hydride-N-methylmorpholine- N-oxide complex (Ramachandran, P. V.; Reddy, M. V.; Rudd, M. T. Chem. Commun. 1999, 1979-1980) followed by addition of benzaldehyde afforded a 1:1 mixture of stereoisomeric (E)- and (Z)-alkenes. This stereochemical outcome is consistent with the intermediacy of an aluminum allenolate, as previously discussed by Tsuda et al. (Tsuda, T.; Yoshida, T.; Saegusa, T. J. Org. Chem. 1988, 53, 1037-1040).
    • In the course of developing a synthetic route to the deuteriumlabeled substrates, we made the following observation: treatment of 3-deuteriopropiolate with diisobutylaluminum hydride-N-methylmorpholine- N-oxide complex (Ramachandran, P. V.; Reddy, M. V.; Rudd, M. T. Chem. Commun. 1999, 1979-1980) followed by addition of benzaldehyde afforded a 1:1 mixture of stereoisomeric (E)- and (Z)-alkenes. This stereochemical outcome is consistent with the intermediacy of an aluminum allenolate, as previously discussed by Tsuda et al. (Tsuda, T.; Yoshida, T.; Saegusa, T. J. Org. Chem. 1988, 53, 1037-1040).
  • 22
    • 37049075524 scopus 로고    scopus 로고
    • Meth-Cohn et al. have reported examples of both stereospecific and non-stereospecific epoxidations with lithium tert-butylperoxide in THF ( (a) Clark, C.; Hermans, P.; Meth-Cohn, O.; Moore, C.; Taljaard, H. C.; van Vuuren, G. J. Chem. Soc., Chem. Commun. 1986, 1378-1380.
    • Meth-Cohn et al. have reported examples of both stereospecific and non-stereospecific epoxidations with lithium tert-butylperoxide in THF ( (a) Clark, C.; Hermans, P.; Meth-Cohn, O.; Moore, C.; Taljaard, H. C.; van Vuuren, G. J. Chem. Soc., Chem. Commun. 1986, 1378-1380.
  • 23
    • 66149160282 scopus 로고    scopus 로고
    • Meth- Cohn, O.; Moore, C.; Taljaard, H. C. J. Chem. Soc., Perkin Trans. 1, 1988 2663-2674.For example, these authors found that epoxidation of phenyl (Z)-2-phenylethenylsulfone proceeded with retention of stereochemistry, providing the corresponding cis epoxide in 90% yield, while epoxidation of di-tert-butyl maleate
    • Meth- Cohn, O.; Moore, C.; Taljaard, H. C. J. Chem. Soc., Perkin Trans. 1, 1988 2663-2674).For example, these authors found that epoxidation of phenyl (Z)-2-phenylethenylsulfone proceeded with retention of stereochemistry, providing the corresponding cis epoxide in 90% yield, while epoxidation of di-tert-butyl maleate
  • 24
    • 66149185334 scopus 로고    scopus 로고
    • proceeded with inversion of stereochemistry, providing the trans epoxide in 60% yield. We have examined the epoxidation of the latter substrate under the optimized conditions described above and found that the cis epoxide was formed with g95% stereospecificity in 80% yield after column chromatography see the Supporting Information
    • proceeded with inversion of stereochemistry, providing the trans epoxide in 60% yield. We have examined the epoxidation of the latter substrate under the optimized conditions described above and found that the cis epoxide was formed with g95% stereospecificity in 80% yield after column chromatography (see the Supporting Information).
  • 27
    • 33751552796 scopus 로고
    • For discussions of the diastereoselectivities of dihydroxylations of closely related substrates, see: a
    • For discussions of the diastereoselectivities of dihydroxylations of closely related substrates, see: (a) Evans, D. A.; Kaldor, S. W. J. Org. Chem. 1990, 55, 1698-1700.
    • (1990) J. Org. Chem , vol.55 , pp. 1698-1700
    • Evans, D.A.1    Kaldor, S.W.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.