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Volumn 316, Issue 5824, 2007, Pages 582-585

Enantioselective organocatalysis using SOMO activation

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE DERIVATIVE; ALLYL COMPOUND; ENAMINE; HYDROCARBON; OXIDIZING AGENT; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; RADICAL;

EID: 34247565955     PISSN: 00368075     EISSN: 10959203     Source Type: Journal    
DOI: 10.1126/science. 1142696     Document Type: Article
Times cited : (598)

References (32)
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    • (2000) Catalytic Asymmetric Synthesis
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    • and references therein
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    • (1995) Handbook of Chemistry and Physics , pp. 220-221
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    • DFT calculations were performed at the B3LYP/6-311+G(2d,p)//B3LYP/6- 31G(d) level of theory using Gaussian 03 software (1-4).
    • DFT calculations were performed at the B3LYP/6-311+G(2d,p)//B3LYP/6- 31G(d) level of theory using Gaussian 03 software (1-4).
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    • P. Renaud, M. P. Sibi, Eds., Radicals in Organic Synthesis (Wiley-VHC, Weinheim, Germany, 2001), vol. 2, pp. 144-205.
    • (2001) Radicals in Organic Synthesis , vol.2 , pp. 144-205
  • 20
    • 34247587882 scopus 로고    scopus 로고
    • Organocatalysis in combination with organometallic catalysis has previously been applied to the nonasymmetric allylation of aldehydes
    • Organocatalysis in combination with organometallic catalysis has previously been applied to the nonasymmetric allylation of aldehydes.
  • 24
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    • Materials and methods are available as supporting online material on Science Online.
    • Materials and methods are available as supporting online material on Science Online.
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    • Mechanistically, we speculate that addition of the Π-rich allylsilane to the radical-cation species results in the formation of a β-silyl radical that undergoes rapid oxidation to the corresponding β-silyl cation before silyl elimination with concomitant olefin formation
    • Mechanistically, we speculate that addition of the Π-rich allylsilane to the radical-cation species results in the formation of a β-silyl radical that undergoes rapid oxidation to the corresponding β-silyl cation before silyl elimination with concomitant olefin formation.
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    • 2).
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    • Bench-grade DME was found to contain sufficient water to achieve optimal results. The exclusion of water by the use of rigorously dried DME results in substantially lower chemical yields
    • Bench-grade DME was found to contain sufficient water to achieve optimal results. The exclusion of water by the use of rigorously dried DME results in substantially lower chemical yields.
  • 29
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    • The coupling of octanal with allylsilane using acetone as the bulk medium provided the corresponding allylation product in 79% ee 75% conversion after 24 hours
    • The coupling of octanal with allylsilane using acetone as the bulk medium provided the corresponding allylation product in 79% ee (75% conversion after 24 hours).
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    • M. P. Sibi, M. Hasegawa, J. Am. Chem. Soc. 129, 395 (2007); published online 16 March 2007 (10.1021/ja069245n).
    • M. P. Sibi, M. Hasegawa, J. Am. Chem. Soc. 129, 395 (2007); published online 16 March 2007 (10.1021/ja069245n).
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    • We thank R. A. Pascal for invaluable assistance in performing Gaussian DFT calculations and M. Amatore for a late-stage experimental contribution. Financial support was provided by NIH National Institute of General Medical Sciences (grant R0l GM078201-01-01) and by gifts from Amgen, Merck Research Laboratories, and the Astellas Foundation USA. T.D.B. is grateful for a Novartis predoctoral fellowship, J.-B.H. is grateful for a KRF postdoctoral fellowship, and K.A. is grateful for a Merck overseas postdoctoral fellowship
    • We thank R. A. Pascal for invaluable assistance in performing Gaussian DFT calculations and M. Amatore for a late-stage experimental contribution. Financial support was provided by NIH National Institute of General Medical Sciences (grant R0l GM078201-01-01) and by gifts from Amgen, Merck Research Laboratories, and the Astellas Foundation USA. T.D.B. is grateful for a Novartis predoctoral fellowship, J.-B.H. is grateful for a KRF postdoctoral fellowship, and K.A. is grateful for a Merck overseas postdoctoral fellowship.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.