Linked Life Data

16351120

Source:http://linkedlifedata.com/resource/pubmed/id/16351120

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
50
pubmed:dateCreated
2005-12-14
pubmed:abstractText
Palladium(II)-catalyzed aerobic oxidative amination of styrene with oxazolidinone proceeds with catalyst-controlled regioselectivity: (CH3CN)2PdCl2 (1) and (Et3N)2PdCl2 (2) catalyze formation of the anti-Markovnikov and Markovnikov enecarbamate products, 3 and 4, respectively. Kinetic studies and deuterium kinetic isotope effects demonstrate that these two reactions possess different rate-limiting steps, and the data indicate that the product regiochemistry arises from the presence or absence of an effective Brønsted base in the reaction. In the presence of a Brønsted base such as triethylamine or acetate, the kinetically preferred Markovnikov aminopalladation adduct of styrene is trapped via rapid deprotonation of a zwitterionic intermediate and leads to formation of 4. In the absence of an effective Brønsted base, however, slow deprotonation of this adduct enables aminopalladation to be reversible, and product formation proceeds through the thermodynamically preferred anti-Markovnikov aminopalladation adduct to yield 3.
pubmed:grant
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Dec
pubmed:issn
0002-7863
pubmed:author
pubmed:issnType
Print
pubmed:day
21
pubmed:volume
127
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
17888-93
pubmed:dateRevised
2007-11-14
pubmed:meshHeading
pubmed:year
2005
pubmed:articleTitle
Brønsted base-modulated regioselectivity in the aerobic oxidative amination of styrene catalyzed by palladium.
pubmed:affiliation
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't, Research Support, N.I.H., Extramural