Abstract
Certain B-alkyl-9-borabicyclo[3.3.1]nonanes (9-BBN) reduce benzaldehyde to benzyl alcohol under exceptionally mild conditions. Factors which contribute to a high rate of reaction include: an increase in the degree of substitution at the position β to the boron (isobutyl > 1-butyl >> ethyl), the ability of the alkyl group to form a syn-planar B-C-C-H conformation (cyclopentyl {reversed tilde equals} norbornyl > sec-butyl >> cyclohexyl), and the presence of an electron-withdrawing para-substituent on the benzaldehyde (p-Cl > p-H > p-CH3O). The B-alkyl group is transformed into an olefin as the benzaldehyde is reduced. Elimination takes place predominantly if not exclusively towards the more highly substituted β hydrogen. The reaction obeys second order kinetics. The observations are consistent with a cyclic mechanism rather than a dehydroboration-reduction pathway.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 203-211 |
| Number of pages | 9 |
| Journal | Journal of Organometallic Chemistry |
| Volume | 156 |
| Issue number | 1 |
| DOIs | |
| State | Published - Aug 15 1978 |
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ASJC Scopus subject areas
- Biochemistry
- Chemical Engineering (miscellaneous)
- Inorganic Chemistry
- Organic Chemistry
- Physical and Theoretical Chemistry
- Materials Science (miscellaneous)
- Materials Chemistry
Cite this
The reaction of B-alkyl-9-borabicyclo[3.3.1]nonanes with aldehydes and ketones. A facile elimination of the alkyl group by aldehydes. / Midland, M. Mark; Tramontano, Alfonso; Zderic, Stephen A.
In: Journal of Organometallic Chemistry, Vol. 156, No. 1, 15.08.1978, p. 203-211.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - The reaction of B-alkyl-9-borabicyclo[3.3.1]nonanes with aldehydes and ketones. A facile elimination of the alkyl group by aldehydes
AU - Midland, M. Mark
AU - Tramontano, Alfonso
AU - Zderic, Stephen A.
PY - 1978/8/15
Y1 - 1978/8/15
N2 - Certain B-alkyl-9-borabicyclo[3.3.1]nonanes (9-BBN) reduce benzaldehyde to benzyl alcohol under exceptionally mild conditions. Factors which contribute to a high rate of reaction include: an increase in the degree of substitution at the position β to the boron (isobutyl > 1-butyl >> ethyl), the ability of the alkyl group to form a syn-planar B-C-C-H conformation (cyclopentyl {reversed tilde equals} norbornyl > sec-butyl >> cyclohexyl), and the presence of an electron-withdrawing para-substituent on the benzaldehyde (p-Cl > p-H > p-CH3O). The B-alkyl group is transformed into an olefin as the benzaldehyde is reduced. Elimination takes place predominantly if not exclusively towards the more highly substituted β hydrogen. The reaction obeys second order kinetics. The observations are consistent with a cyclic mechanism rather than a dehydroboration-reduction pathway.
AB - Certain B-alkyl-9-borabicyclo[3.3.1]nonanes (9-BBN) reduce benzaldehyde to benzyl alcohol under exceptionally mild conditions. Factors which contribute to a high rate of reaction include: an increase in the degree of substitution at the position β to the boron (isobutyl > 1-butyl >> ethyl), the ability of the alkyl group to form a syn-planar B-C-C-H conformation (cyclopentyl {reversed tilde equals} norbornyl > sec-butyl >> cyclohexyl), and the presence of an electron-withdrawing para-substituent on the benzaldehyde (p-Cl > p-H > p-CH3O). The B-alkyl group is transformed into an olefin as the benzaldehyde is reduced. Elimination takes place predominantly if not exclusively towards the more highly substituted β hydrogen. The reaction obeys second order kinetics. The observations are consistent with a cyclic mechanism rather than a dehydroboration-reduction pathway.
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UR - http://www.scopus.com/inward/citedby.url?scp=0345396306&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(00)84877-9
DO - 10.1016/S0022-328X(00)84877-9
M3 - Article
AN - SCOPUS:0345396306
VL - 156
SP - 203
EP - 211
JO - Journal of Organometalic Chemistry
JF - Journal of Organometalic Chemistry
SN - 0022-328X
IS - 1
ER -