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Volumn 13, Issue 6, 2011, Pages 1478-1481

Thermodynamic control of 1,3-boratropic shifts of α- And γ-stannyl-substituted allylboranes: Hyperconjugation outweighs steric effects

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; ALDEHYDE; ALKADIENE; ALLENE; BORANE DERIVATIVE; ORGANOTIN COMPOUND;

EID: 79952578720     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol2001599     Document Type: Article
Times cited : (19)

References (41)
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    • Roush, W. R. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, U.K., 1991; Vol. 2, p 1.
    • (1991) Comprehensive Organic Synthesis , vol.2 , pp. 1
    • Roush, W.R.1
  • 21
    • 79952576246 scopus 로고    scopus 로고
    • Gaussian 03, Revision D.01; Gaussian, Inc.: Wallingford, CT,. See the Supporting Information for the full reference.
    • Frisch, M. J. Gaussian 03, Revision D.01; Gaussian, Inc.: Wallingford, CT, 2004. See the Supporting Information for the full reference.
    • (2004)
    • Frisch, M.J.1
  • 22
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    • Jaguar, version 7.7, Schrodinger, LLC, New York, NY.
    • Jaguar, version 7.7, Schrodinger, LLC, New York, NY, 2010.
    • (2010)
  • 23
    • 79952588477 scopus 로고    scopus 로고
    • Gaussian 09, Revision A.02; Gaussian, Inc.: Wallingford, CT,. See the Supporting Information for full reference.
    • Frisch, M. J. Gaussian 09, Revision A.02; Gaussian, Inc.: Wallingford, CT, 2009. See the Supporting Information for full reference.
    • (2009)
    • Frisch, M.J.1
  • 25
    • 79952578516 scopus 로고    scopus 로고
    • Keywords gdftmed = -14, gdftfine = -14, and gdftgrad = -14 were used to generate a very dense grid.
    • Keywords gdftmed = -14, gdftfine = -14, and gdftgrad = -14 were used to generate a very dense grid.
  • 27
    • 79952591764 scopus 로고    scopus 로고
    • Hydroboration of allenylstannane 1 (1 equiv) with 9-BBN (0.5 equiv) was carried out at 0 °C for 5 h. The structure of the resulting allylborane was deduced based on the allylboration product of hydrocinnamaldehyde. See the Supporting Information for details.
    • Hydroboration of allenylstannane 1 (1 equiv) with 9-BBN (0.5 equiv) was carried out at 0 °C for 5 h. The structure of the resulting allylborane was deduced based on the allylboration product of hydrocinnamaldehyde. See the Supporting Information for details.
  • 28
    • 79952587652 scopus 로고    scopus 로고
    • Diastereoselective rearrangment of (Z)-δ-stannylallylborane 2a can result in either 3a or 3a′. We previously showed (ref 2) that the 1,3-boratropic shift transition state leading to 3a is 2.2 kcal/mol lower than the barrier leading to 3a′. However, 3a′ is slightly more stable thermodynamically than 3a (ca. 2:1 experimentally).
    • Diastereoselective rearrangment of (Z)-δ-stannylallylborane 2a can result in either 3a or 3a′. We previously showed (ref 2) that the 1,3-boratropic shift transition state leading to 3a is 2.2 kcal/mol lower than the barrier leading to 3a′. However, 3a′ is slightly more stable thermodynamically than 3a (ca. 2:1 experimentally).


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