110507-84-1Relevant academic research and scientific papers
The regio- and stereospecific intermolecular dehydrative alkoxylation of allylic alcohols catalyzed by a gold(I) N-heterocyclic carbene complex
Mukherjee, Paramita,Widenhoefer, Ross A.
supporting information, p. 3437 - 3444 (2013/07/05)
A 1:1 mixture of [AuCl(IPr)] (IPr=1,3-bis(2,6-diisopropylphenyl)imidazol-2- ylidine) and AgClO4 catalyzes the intermolecular dehydrative alkoxylation of primary and secondary allylic alcohols with aliphatic primary and secondary alcohols to for
Simple protocol for enhanced (E)-selectivity in Julia-Kocienski reaction
Pospí?il, Ji?í
supporting information; experimental part, p. 2348 - 2352 (2011/05/16)
A short and efficient Julia-Kocienski olefination protocol, based upon the use of chelating agents (18-crown-6 or TDA-1 for K+; 12-crown-4 or HMPA for Li+), was developed. This protocol enhances the (E)-selectivity of the reaction an
In situ generated bulky palladium hydride complexes as catalysts for the efficient isomerization of olefins. Selective transformation of terminal alkenes to 2-alkenes
Gauthier, Delphine,Lindhardt, Anders T.,Olsen, Esben P. K.,Overgaard, Jacob,Skrydstrup, Troels
supporting information; experimental part, p. 7998 - 8009 (2010/08/04)
Application of an in situ generated bulky palladium(II) hydride catalyst obtained from a 1:1:1 mixture of Pd(dba)2, P(tBu)3, and isobutyryl chloride provides an efficient protocol for the isomerization and migration of a variety of olefins. In addition to the isomerization of (Z)- to (E)-olefins, the conjugative migration of allylbenzenes, allyl ethers, and amines was effectively achieved in near-quantitative yields and with excellent functional group tolerance. Catalyst loadings in the range of 0.5-1.0 mol % were typically applied, but even loadings as low as 0.25 mol % could be achieved when the reactions were performed under neat conditions. More interestingly, the investigated catalyst proved to be selective for converting terminal alkenes to 2-alkenes. This one-carbon migration process for monosubstituted olefins provides an alternative catalyst, which bridges the gap between the allylation and propenylation/vinylation protocols. Several substrates, including homoallylic alcohols and amines, were selectively transformed into their corresponding 2-alkenes, and examples using enantiomerically enriched substrates provided products without epimerization at the allylic stereogenic carbon centers. Finally, some mechanistic investigations were undertaken to understand the nature of the active in situ generated Pd-H catalyst. These studies revealed that the catalytic system is highly dependent on the large steric demand of the P(tBu)3 ligand. The use of an alternative ligand, cataCXium PinCy, also proved effective for generating an active catalyst, and it was demonstrated in some cases to display better selectivity for the one-carbon shifts of terminal olefins. A possible intermediate involved in the preparation of the active catalyst was characterized by its single-crystal X-ray structure, which revealed a monomeric tricoordinated palladium(II) acyl complex, bearing a chloride ligand.
General method for the palladium-catalyzed allylation of aliphatic alcohols
Haight, Anthony R.,Stoner, Eric J.,Peterson, Matthew J.,Grover, Vandana K.
, p. 8092 - 8096 (2007/10/03)
A palladium catalysis-mediated approach to coupling aliphatic alcohols with allyl carbonates has been developed. The method allows for the allylation of primary, secondary, and tertiary alcohols efficiently under mild conditions. Limitations were explored as well as the asymmetric application of the chemistry. Regiochemical and olefin geometry was controlled in the coupling of unsymmetrical allylating agents. Transient allyl carbonates were observed in the coupling, which comprised the trans-carboxylation of the allyl-carbonate with the requisite alcohol.
