The Rh(I)-catalyzed reaction of siloxyvinylcyclopropanes and diazoesters leads to the formation of siloxyvinylcyclobutane and 1,4-diene derivatives. With [Rh(cod)Cl] as the catalyst, the formation of 1,4-diene was favored over the formation of siloxyvinylcyclobutane. By changing the catalyst to [Rh(cod)OTf], siloxyvinylcyclobutane derivatives are formed with excellent chemoselectivities and in moderate to good yields. The alkene products are also obtained as single configured isomers. A detailed mechanism for this transformation is proposed on the basis of mechanistic experiments and DFT calculations. The effect of catalysts on the chemoselectivity of these reactions is also examined computationally.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jacs.0c08089 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Mechanism and origins of regio- and enantioselectivities in RhI-catalyzed hydrogenative couplings of 1,3-diynes and activated carbonyl partners: intervention of a cumulene intermediate.
Chemistry
March 2011
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569, USA.
The mechanism of the rhodium-catalyzed reductive coupling of 1,3-diynes and vicinal dicarbonyl compounds employing H(2) as reductant was investigated by density functional theory. Oxidative coupling through 1,4-addition of the Rh(I)-bound dicarbonyl to the conjugated diyne via a seven-membered cyclic cumulene transition state leads to exclusive formation of linear adducts. Diyne 1,4-addition is much faster than the 1,2-addition to simple alkynes.
View Article and Find Full Text PDFRhI-catalyzed aldol-type reaction of organonitriles under mild conditions.
Chem Commun (Camb)
May 2008
Department of Chemistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602, Japan.
An aldol-type reaction of organonitriles with aldehydes was catalyzed by a RhI(OR) species under ambient conditions, and the reaction displayed a broad substrate scope with respect to both organonitrile and aldehyde components.
View Article and Find Full Text PDFStereoselective RhI-catalyzed tandem conjugate addition of boronic acids-Michael cyclization.
Org Lett
January 2008
Departamento de Química Orgánica, Facultad de Química, Universidad Complutense, 28040-Madrid, Spain.
The first examples of the stereoselective sequence RhI-catalyzed tandem conjugate addition of boronic acids to enones-Michael cyclization, is reported. The reaction is carried out in dioxane-H2O at rt, and 1,2,3-trisubstituted indans are obtained in a highly regio- and stereoselective fashion.
View Article and Find Full Text PDFStereoselective conjugate addition of aryl- and alkenylboronic acids to acyclic gamma,delta-oxygen-substituted alpha,beta-enoates.
Org Lett
August 2007
Departamento de Química Orgánica, Facultad de Química, Universidad Complutense, 28040-Madrid, Spain.
The substrate-controlled RhI-catalyzed conjugate addition of aryl- and alkenylboronic acids to alpha,beta-unsaturated esters which bear gamma- and delta-oxygen substituents takes place in a highly anti diastereoselective fashion either when using gamma-hydroxyl unprotected starting materials or when the gamma-oxygen substituent is protected with a nonbulky group. The delta-oxygen substituent plays a role in the stereoselectivity of the reaction, and better results are obtained when this OH-group is protected.
View Article and Find Full Text PDFRhI-catalyzed C-C bond activation: seven-membered ring synthesis by a [6+1] carbonylative ring-expansion reaction of allenylcyclobutanes.
Angew Chem Int Ed Engl
June 2006
Department of Chemistry, Department of Molecular Pharmacology, Stanford University, Stanford, CA 94305-5080, USA.
Want AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!