Linked Life Data

20449093

Source:http://linkedlifedata.com/resource/pubmed/id/20449093

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
29
pubmed:dateCreated
2010-5-7
pubmed:abstractText
The study thoroughly examines the Gibbs free energy surfaces of a new mechanism for reduction of ketones/aldehydes by tris(pentafluorophenyl)borane (1) and H(2). Key elements of the proposed mechanism are the proton and the hydride transfer steps similar to Stephan's catalytic reduction of imines by 1. The proton is transferred to the ketone/aldehyde in the process of H(2) cleavage by the carbonyl-borane couple and the hydride is transferred in a nucleophilic attack on the carbonyl carbon by the hydridoborate in the ionic pair, [HOCRR'](+)[HB(C(6)F(5))(3)](-). The in solvent Gibbs free energy barriers of H(2) splitting by adducts of B(C(6)F(5))(3) with acetone, acetophenone and benzaldehyde are predicted to be in the range of 24.5 +/- 2.5 kcal mol(-1), which corresponds to potential energy barriers in the range of 17.0 +/- 2.0 kcal mol(-1). Significantly lower barrier of H(2) activation is predicted in cases of bulky ketones such as 2,2,4,4-tetramethylpentan-3-one. With respect to the hydridoborate intermediate, the nucleophilic attack on the activated carbon is predicted to have a relatively low barrier for the sterically unhindered substrates, while this barrier is considerably higher for the sterically encumbered substrates. Since the formation of the hydridoborate intermediates is found to be endothermic, the transition state of the nucleophilic attack is the highest point of the computed energy profile for all tested substrates. Overall, according to in solvent density function calculations the proposed reduction of "compact" ketones/aldehydes by 1 and H(2) is allowed both thermodynamically and kinetically at elevated temperature, but it is expected to be slower and more substrate specific than the corresponding reduction of imines.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Aug
pubmed:issn
1477-9234
pubmed:author
pubmed:issnType
Electronic
pubmed:day
7
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
5780-6
pubmed:meshHeading
pubmed:year
2009
pubmed:articleTitle
On the possibility of catalytic reduction of carbonyl moieties with tris(pentafluorophenyl)borane and H2: a computational study.
pubmed:affiliation
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91, Stockholm, Sweden.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't