Origin of Thermodynamic versus Kinetic Control of Allene Hydroboration with 9-Borabicyclo[3.3.1]nonane and 10(R)-Trimethylsilyl-9-Borabicyclo[3.3.2]decane

Daniel H. Ess; Jeremy Kister; Ming Chen; William R. Roush

doi:10.1021/ol902364d

journal article Nov 09, 2009

Origin of Thermodynamic versus Kinetic Control of Allene Hydroboration with 9-Borabicyclo[3.3.1]nonane and 10(R)-Trimethylsilyl-9-Borabicyclo[3.3.2]decane

Daniel H. Ess

Jeremy Kister Ming Chen

William R. Roush

Organic Letters Vol. 11 No. 23 pp. 5538-5541 · American Chemical Society (ACS)

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bThe S-configuration of1awas used in all calculations.

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Jaguar, version7.5;Schrodinger, LLC:New York, 2008.All stationary points were verified as minima or first-order saddle points by calculation of the full Hessian. Enthalpy and free energy corrections were applied at 298 K and all energies are reported in kcal/mol.

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This level of theory gives energetics in agreement with CCSD(T) theory for [1,3]-boratropic shifts. See:

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The other extreme on a closed-shell More O’Ferrall-Jencks diagram would be a charge-separated boracyclobutane. Between the ground state and TS, the NBO charges change most significantly at the boron center, which loses positive charge.

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In bothTS-Z6andTS-E6, allene2capproaches the borane face opposite of the 10-TMS group. Hydroboration from the side nearest the 10-TMS group is disfavored by ∼3 kcal/mol. Also see:

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This prediction is in accord with the experimental observation that Ipc2BH hydroboration of 1,1-disubstituted allenes shows high kinetic control. See:

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Substituent effects on the barrier for the [1,3]-boratropic shift of dimethyl borane is given in theSupporting Information.

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The C−Si bond length decreases by only 0.004 Å betweenZ-7(1.930 Å) andTS-Z7(1.934 Å). The barrier for rearrangement ofTS-Z7decreases by 6.4 kcal/mol when the 10-TMS group is deleted and replaced with hydrogen. When the 10-TMS is is deleted and replaced with SiH3, the barrier is intermediate between TMS and hydrogen because there is both a small hyperconjugative effect and reduced steric interactions.

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Details

Published: Nov 09, 2009
Vol/Issue: 11(23)
Pages: 5538-5541

Authors

D

Daniel H. Ess

Department of Chemistry, The Scripps Research Institute, Jupiter, Florida 33458

J

Jeremy Kister

Department of Chemistry, The Scripps Research Institute, Jupiter, Florida 33458

M

Ming Chen

Department of Chemistry, The Scripps Research Institute, Jupiter, Florida 33458

W

William R. Roush

Department of Chemistry, The Scripps Research Institute, Jupiter, Florida 33458

Cite This Article

Daniel H. Ess, Jeremy Kister, Ming Chen, et al. (2009). Origin of Thermodynamic versus Kinetic Control of Allene Hydroboration with 9-Borabicyclo[3.3.1]nonane and 10(R)-Trimethylsilyl-9-Borabicyclo[3.3.2]decane. Organic Letters, 11(23), 5538-5541. https://doi.org/10.1021/ol902364d

Origin of Thermodynamic versus Kinetic Control of Allene Hydroboration with 9-Borabicyclo[3.3.1]nonane and 10(R)-Trimethylsilyl-9-Borabicyclo[3.3.2]decane

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