Mild-condition synthesis of allenes from alkynes and aldehydes mediated by tetrahydroisoquinoline (THIQ).

A practical 1,2,3,4-tetrahydroisoquinoline (THIQ)-mediated synthesis of 1,3-disubstituted allenes from terminal alkynes and aldehydes under mild conditions in the presence of CuBr first and then ZnI2 was reported. This telescoped allene synthesis reaction includes three consecutive steps and two reactions: first, a room-temperature CuBr-catalyzed synthesis of propargylamines, exo-yne-THIQs, from terminal alkynes, aldehydes, and THIQ, then filtration of the CuBr catalyst, and finally the ZnI2-mediated allene synthesis from the generated exo-yne-THIQs under mild conditions (either at room temperature or heating at 50 or 75 °C). A wide range of aliphatic or aromatic aldehydes and terminal alkynes are tolerated, affording the allene products in up to 92% yield.

CuI-catalyzed C1-alkynylation of tetrahydroisoquinolines (THIQs) by A3 reaction with tunable iminium ions.

A CuI-catalyzed A(3) (amines, aldehydes and alkynes) reaction of tetrahydroisoquinolines (THIQs), aldehydes, and alkynes to give C1-alkynylated THIQ products (endo-yne-THIQs) was developed. This redox neutral C1-alkynylation of THIQs, which was conducted under mild conditions, has a broad scope for the used aldehydes and alkynes. It was proposed that the A(3) reaction first generates in situ exo-iminium ions, which then isomerize to endo-iminium ions and react with copper acetylides to give the endo alkynylated THIQs (endo-yne-THIQs).

DFT study on the mechanism and stereochemistry of the Petasis-Ferrier rearrangements.

The Petasis-Ferrier rearrangement is a very important and useful reaction for the synthesis of multifunctional tetrahydrofurans and tetrahydropyrans from easily synthesized enol acetals. Here we report our DFT investigation of the detailed reaction mechanism of the Petasis-Ferrier rearrangement, proposing that the active promoting species in this reaction is the cationic aluminum species, instead of the usually considered neutral Lewis acid (this will give very high activation energies and cannot explain why the Petasis-Ferrier rearrangements usually take place at low temperature or under mild conditions). Calculations indicated that the mechanisms of the Petasis-Ferrier rearrangements for the formations of five- and six-membered rings are different.

Rh(I)-catalyzed [5+1] cycloaddition of vinylcyclopropanes and CO for the synthesis of α,β- and β,γ-cyclohexenones.

A cationic Rh(I)-catalyzed [5 + 1] cycloaddition of vinylcyclopropanes and CO has been developed, affording either β,γ-cyclohexenones as major products or α,β-cyclohexenones exclusively, under different reaction conditions.

Reaction of alpha-ene-vinylcyclopropanes: type II intramolecular [5+2] cycloaddition or [3+2] cycloaddition?

Exposure of alpha-ene-VCPs to catalytic [Rh(dppm)]SbF(6) led to the discovery of a novel Rh(I)-catalyzed [3+2] reaction, which was shown to be efficient for the construction of 5/6- and 5/7-bicyclic compounds rather than the anticipated type II [5+2] products.

Palladium-catalyzed alkenylation of quinoline-N-oxides via C-H activation under external-oxidant-free conditions.

The direct cross-coupling of quinoline-N-oxides with olefin derivatives has been realized using palladium acetate as the catalyst in the absence of external ligand and oxidant to give the corresponding 2-alkenylated quinolines and 1-alkenylated isoquinolines chemo- and regioselectively in 27-95% yield. The catalytic process is proposed to proceed via direct C-H bond activation of the quinoline-N-oxide with Pd(OAc)(2) followed by Heck coupling with the olefin. The resultant N-oxide of the alkenylated quinoline can oxidize the reduced Pd(0) to regenerate the Pd(II) active species and simultaneously release the 2-alkenylated quinoline without using any external oxidants and reductants.