Claisen rearrangement over the past nine decades.

Enantiomerically pure cyclobutane derivatives and their use in organic synthesis.

Natural Science Foundation of China [30530080]; Ministry of Science and Technology of China [2007AA09Z403]; Department of Science and Technology of Shandong Province [2006GG2205023]

http://ir.yic.ac.cn/bitstream/133337/9046/1/Halogenated%20Organic%20Molecules%20of%20Rhodomelaceae%20Origin-Chemistry%20and%20Biology.pdf

Halogenated Organic Molecules of Rhodomelaceae Origin: Chemistry and Biology

The mechanism for the rhodium-catalyzed decarbonylation of aldehydes was investigated by experimental techniques (Hammett studies and kinetic isotope effects) and extended by a computational study (DFT calculations). For both benzaldehyde and phenyl acetaldehyde derivatives, linear Hammett plots were obtained with positive slopes of +0.79 and +0.43, respectively, which indicate a buildup of negative charge in the selectivity-determining step. The kinetic isotope effects were similar for these substrates (1.73 and 1.77 for benzaldehyde and phenyl acetaldehyde, respectively), indicating that similar mechanisms are operating. A DFT (B3LYP) study of the catalytic cycle indicated a rapid oxidative addition into the C(O)−H bond followed by a rate-limiting extrusion of CO and reductive elimination. The theoretical kinetic isotope effects based on this mechanism were in excellent agreement with the experimental values for both substrates, but only when migratory extrusion of CO was selected as the rate-determinin...

The mechanism for the rhodium-catalyzed decarbonylation of aldehydes: a combined experimental and theoretical study.

http://www.rsc.org/suppdata/CC/b8/b813171f/b813171f.pdf

The iridium-catalyzed decarbonylation of aldehydes under mild conditions

Synthetic and mechanistic studies of the retro-Claisen rearrangement. 4. An application to the total synthesis of (+)-Laurenyne.

Synthetic and Mechanistic Studies of the Retro-Claisen Rearrangement. 3. A Route to Enantiomerically Pure Vinyl Cyclobutane Diesters via a Highly Diastereoselective Syn SN2‘ Reaction and Their Rearrangement to Enantiomerically Pure Dihydrooxacenes

Synthetic and Mechanistic Studies of the Retro‐Claisen Rearrangement. Part 3. A Route to Enantiomerically Pure Vinyl Cyclobutane Diesters via a Highly Diastereoselective syn SN2′ Reaction and Their Rearrangement to Enantiomerically Pure Dihydrooxacenes.

Michael R. Reeder

Papers

Synthetic and mechanistic studies of the retro-Claisen rearrangement. 4. An application to the total synthesis of (+)-Laurenyne.

Synthetic and Mechanistic Studies of the Retro-Claisen Rearrangement. 3. A Route to Enantiomerically Pure Vinyl Cyclobutane Diesters via a Highly Diastereoselective Syn SN2‘ Reaction and Their Rearrangement to Enantiomerically Pure Dihydrooxacenes

Synthetic and Mechanistic Studies of the Retro‐Claisen Rearrangement. Part 3. A Route to Enantiomerically Pure Vinyl Cyclobutane Diesters via a Highly Diastereoselective syn SN2′ Reaction and Their Rearrangement to Enantiomerically Pure Dihydrooxacenes.