메뉴 건너뛰기




Volumn 133, Issue 21, 2011, Pages 8130-8133

N-heterocyclic carbene (NHC)-catalyzed intermolecular hydroacylation of cyclopropenes

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC ALDEHYDE; CYCLOPROPENES; DIASTEREOCONTROL; HIGH YIELD; HYDROACYLATION; MECHANISTIC STUDIES; N-HETEROCYCLIC CARBENES; PRODUCT FORMATION;

EID: 79957750879     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja202594g     Document Type: Article
Times cited : (136)

References (63)
  • 9
    • 0001710837 scopus 로고    scopus 로고
    • For select examples of intramolecular asymmetric Stetter reactions, see
    • For select examples of intramolecular asymmetric Stetter reactions, see: Enders, D.; Breuer, K.; Runsink, J.; Teles, J. H. Helv. Chim. Acta 1996, 79, 1899
    • (1996) Helv. Chim. Acta , vol.79 , pp. 1899
    • Enders, D.1    Breuer, K.2    Runsink, J.3    Teles, J.H.4
  • 35
    • 0001781293 scopus 로고    scopus 로고
    • For reviews on bioactive cyclopropane-containing compounds and its occurrence in natural products, see: Salaün, J. Top. Curr. Chem. 2000, 207, 1
    • (2000) Top. Curr. Chem. , vol.207 , pp. 1
    • Salaün, J.1
  • 44
    • 79957756163 scopus 로고    scopus 로고
    • See the Supporting Information for details
    • See the Supporting Information for details.
  • 47
    • 79957777084 scopus 로고    scopus 로고
    • For an account on the reactivity of mesityl-substituted triazolium salts
    • For an account on the reactivity of mesityl-substituted triazolium salts, see: Chiang, P.-C.; Bode, J. W. TCI Mail 2011, 149, 2
    • (2011) TCI Mail , vol.149 , pp. 2
    • Chiang, P.-C.1    Bode, J.W.2
  • 48
    • 79957780100 scopus 로고    scopus 로고
    • Linear and branched aliphatic aldehydes did not undergo the hydroacylation reaction, affording only traces of the desired product along with the nearly quantitative formation of acyloin even under more forcing conditions (20 mol% of catalyst at 80 °C)
    • Linear and branched aliphatic aldehydes did not undergo the hydroacylation reaction, affording only traces of the desired product along with the nearly quantitative formation of acyloin even under more forcing conditions (20 mol% of catalyst at 80 °C).
  • 49
    • 79957676086 scopus 로고    scopus 로고
    • Attempts to improve the yield or diastereoselectivity by varying the temperature of the reaction proved ineffective
    • Attempts to improve the yield or diastereoselectivity by varying the temperature of the reaction proved ineffective.
  • 50
    • 0035936747 scopus 로고    scopus 로고
    • Only product 3g is previously reported in the literature
    • Only product 3g is previously reported in the literature: Nishimura, T.; Ohe, K.; Uemura, S. J. Org. Chem. 2001, 66, 1455
    • (2001) J. Org. Chem. , vol.66 , pp. 1455
    • Nishimura, T.1    Ohe, K.2    Uemura, S.3
  • 52
    • 79957705575 scopus 로고    scopus 로고
    • Substrates with a combination of electron-richness and steric hindrance gave little amount of the desired product. For example, 2-methoxybenzaldehyde showed less than 20% conversion with 20 mol% of the triazolium catalyst (data not shown)
    • Substrates with a combination of electron-richness and steric hindrance gave little amount of the desired product. For example, 2-methoxybenzaldehyde showed less than 20% conversion with 20 mol% of the triazolium catalyst (data not shown).
  • 53
    • 79957681564 scopus 로고    scopus 로고
    • This result is consistent with our observation that electron-rich aldehydes exhibit lower reactivity
    • This result is consistent with our observation that electron-rich aldehydes exhibit lower reactivity.
  • 54
    • 79957752909 scopus 로고    scopus 로고
    • This is consistent with our hypothesis on the origin of diastereoselectivity, vide infra. See refs 30 and 31
    • This is consistent with our hypothesis on the origin of diastereoselectivity, vide infra. See refs 30 and 31.
  • 55
    • 79957669334 scopus 로고    scopus 로고
    • 3 showed no detectable formation of the hydroacylated product 3a, see ref 15
    • 3 showed no detectable formation of the hydroacylated product 3a, see ref 15.
  • 57
    • 79957746226 scopus 로고    scopus 로고
    • It amounted to only 85%, most likely due to scrambling with the proton of triazolium salt 7a in the equilibrating process between benzoin and retro-benzoin
    • It amounted to only 85%, most likely due to scrambling with the proton of triazolium salt 7a in the equilibrating process between benzoin and retro-benzoin.
  • 58
    • 49649083861 scopus 로고    scopus 로고
    • Prepared by adapting a known procedure: Alnasleh, B. K.; Sherrill, W. M.; Rubin, M. Org. Lett. 2008, 10, 3231 See Supporting Information for more details and complete characterization
    • (2008) Org. Lett. , vol.10 , pp. 3231
    • Alnasleh, B.K.1    Sherrill, W.M.2    Rubin, M.3
  • 59
    • 0001289430 scopus 로고
    • Because cyclopropyl anions are observed to be configurationally stable (see;;), anti -deuterium incorporation would have been observed based on a stepwise mechanism. (8b) Alternatively, it is also possible that, in a stepwise addition process, formation of the negative charge occurs syn to the Breslow intermediate for electrostatic stabilization. The corresponding stepwise mechanism therefore cannot at this point be excluded
    • Because cyclopropyl anions are observed to be configurationally stable (see Walborsky, H. M.; Impastato, F. J.; Young, A. E. J. Am. Chem. Soc. 1964, 86, 3283), anti -deuterium incorporation would have been observed based on a stepwise mechanism. (8b) Alternatively, it is also possible that, in a stepwise addition process, formation of the negative charge occurs syn to the Breslow intermediate for electrostatic stabilization. The corresponding stepwise mechanism therefore cannot at this point be excluded
    • (1964) J. Am. Chem. Soc. , vol.86 , pp. 3283
    • Walborsky, H.M.1    Impastato, F.J.2    Young, A.E.3
  • 60
    • 0028225158 scopus 로고
    • For related noncatalytic additions to electron-neutral alkenes proceeding through a five-membered concerted transition state, see: Oppolzer, W.; Spivey, A. C.; Bochet, C. G. J. Am. Chem. Soc. 1994, 116, 3139
    • (1994) J. Am. Chem. Soc. , vol.116 , pp. 3139
    • Oppolzer, W.1    Spivey, A.C.2    Bochet, C.G.3
  • 63
    • 79957687204 scopus 로고    scopus 로고
    • 2
    • 2.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.