Linked Life Data

18928284

Source:http://linkedlifedata.com/resource/pubmed/id/18928284

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
45
pubmed:dateCreated
2008-11-6
pubmed:abstractText
An efficient catalytic system has been developed for the synthesis of benzocyclobutenes by C-H activation of methyl groups. The optimal conditions employed a combination of Pd(OAc) 2 and P ( t )Bu 3 as catalyst, K 2CO 3 as the base, and DMF as solvent. A variety of substituted BCB were obtained under these conditions with yields in the 44-92% range, including molecules that are hardly accessible by other methods. The reaction was found limited to substrates bearing a quaternary benzylic carbon, but benzocyclobutenes bearing a tertiary benzylic carbon could be obtained indirectly from diesters by decarboxylation. Reaction substrates bearing a small substituent para to bromine gave an unexpected regioisomer that likely arose from a 1,4-palladium migration process. The formation of this "abnormal" regioisomer could be suppressed by introducing a larger subsituent para to bromine. DFT(B3PW91) calculations on the reaction of 2-bromo-tert-butylbenzene with Pd(P ( t )Bu 3) with different bases (acetate, bicarbonate, carbonate) showed the critical influence of the coordination mode of the base to induce both an easy C-H activation and to allow for a pathway for 1,4-palladium migration. Carbonate is shown to be more efficient than the two other bases because it can abstract the proton easily and at the same time maintain kappa (1)-coordination without extensive electronic reorganization.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Nov
pubmed:issn
1520-5126
pubmed:author
pubmed:issnType
Electronic
pubmed:day
12
pubmed:volume
130
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
15157-66
pubmed:meshHeading
pubmed:year
2008
pubmed:articleTitle
Synthesis of benzocyclobutenes by palladium-catalyzed C-H activation of methyl groups: method and mechanistic study.
pubmed:affiliation
Institut Charles Gerhardt, UMR5253, CNRS-UM2-UM1-ENSCM, case courrier 1501, Place Eugène Bataillon, 34000 Montpellier, France.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't