Linked Life Data

16351104

Source:http://linkedlifedata.com/resource/pubmed/id/16351104

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
50
pubmed:dateCreated
2005-12-14
pubmed:abstractText
The reaction of dodec-11-ene-1,6-diynes or their heteroatom congeners with a hydrosilane catalyzed by Rh(acac)(CO)2 at ambient temperature and pressure of CO gives the corresponding fused 5-7-5 tricyclic products, 5-oxo-1,3a,4,5,7,9-hexahydro-3H-cyclopenta[e]azulenes or their heteroatom congeners, in excellent yields through a unique silicon-initiated cascade carbonylative carbotricyclization (CO-SiCaT) process. It has also been found that the 5-7-5 fused tricyclic products can be obtained from the same type of enediynes and CO through a novel intramolecular [2+2+2+1] cycloaddition process. The characteristics of these two tricyclization processes and the fundamental differences in their reaction mechanisms are discussed. This novel higher-order cycloaddition reaction has also been successfully applied to the tricyclization of undeca-5,10-diyn-1-als, affording the corresponding 5-7-5 fused-ring products bearing a seven-membered lactone moiety. Related [2+2+2] tricyclizations of enediyne and diynal substrates are also discussed. These newly discovered reactions can construct multiple bonds all at once, converting linear starting materials to polycyclic compounds in a single step. Thus, these new processes provide innovative routes to functionalized polycyclic compounds that are useful for the syntheses of natural and unnatural products.
pubmed:grant
pubmed:commentsCorrections
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
17756-67
pubmed:dateRevised
2011-9-26
pubmed:meshHeading
pubmed:year
2005
pubmed:articleTitle
Silicon-initiated carbonylative carbotricyclization and [2+2+2+1] cycloaddition of enediynes catalyzed by rhodium complexes.
pubmed:affiliation
Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York 11794-3400, USA.
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, Non-P.H.S., Research Support, N.I.H., Extramural