67679-11-2

Upstream product

• 874-23-7 2-acetylcyclohexanone 
• 107-18-6 allyl alcohol 
• 1746-13-0 allyl phenyl ether 
• 591-87-7 Allyl acetate 
• 106-95-6 allyl bromide 

Relevant academic research and scientific papers

Direct Allylation of Active Methylene Compounds with Allylic Alcohols by Use of Palladium/Phosphine-Borane Catalyst System

The C?C bond formation between active methylene compounds and allylic alcohols has been newly developed by using a palladium complex as a catalyst together with a phosphine-borane ligand. The best phosphine-borane ligand for this direct allylation has bee

Silica Support-Enhanced Pd-Catalyzed Allylation Using Allylic Alcohols

Although allylation using allylic alcohol is an environmentally-friendly method because of water being the sole byproduct in such reactions, allylic alcohol is one of the most difficult allylating agents in Pd-catalyzed allylation of nucleophiles. In this study, we successfully developed a mesoporous silica-supported Pd complex as an efficient catalyst for the allylation of nucleophiles using allylic alcohols as allylating agents. The allylic alcohol is activated by the silanol group on the support surface, which easily undergoes a π-allylpalladium intermediate formation. The catalytic activity of the supported Pd complex was ca. 9 times higher than that of its homogeneous precursor Pd complex. A highest turnover number of 4500 based on Pd was achieved. Various nucleophiles and allylic alcohol derivatives could be used as substrates. Not only the detailed catalyst structure but also the reaction mechanism including the concerted activation of allylic alcohol by the Pd complex and silanol were investigated by several spectroscopic techniques, such as Pd K-edge XAFS, solid-state NMR, and in-situ FT-IR measurements.

Catalytic C?C Bond Formation Using a Simple Nickel Precatalyst System: Base- and Activator-Free Direct C-Allylation by Alcohols and Amines

A “totally catalytic” nickel(0)-mediated method for base-free direct alkylation of allyl alcohols and allyl amines is reported. The reaction is selective for monoallylation, uses an inexpensive NiII precatalyst system, and requires no activating reagents to be present.

Triethylborane as an efficient promoter for palladium-catalyzed allylation of active methylene compounds with allyl alcohols

Without prior activation of allyl alcohols, allylation of a variety of active methylene compounds with allyl alcohols proceeds smoothly at rt-50°C in the presence of catalytic amounts of Pd(OAc)2 (1-10mol%), Et 3B (30-240mol%), a phosphine ligand (1-20mol%), and a base (0 to 50-60mol%).

Palladium-tetraphosphine complex: An efficient catalyst for allylic substitution and Suzuki cross-coupling

A new tetraphosphine, the cis-cis-cis-1,2,3,4-tetrakis (diphenylphosphinomethyl)cyclopentane (Tedicyp) has been synthesized and used in palladium-catalyzed reactions. This tetraphosphine in combination with [Pd(C3H5)Cl]2 affords a very efficient catalyst for coupling reactions. Turnover numbers of 980 000 for allylic amination, 9 800 000 for allylic alkylation and 97 000 000 for Suzuki cross-coupling can be obtained in the presence of this catalyst.

pH optimization of nucleophilic reactions in water

We present a way of prescribing the pH for a reaction so as to obtain either (a) maximum yield in competition with hydrolysis or (b) selective reaction at either of two sites in such nucleophile-electrophile reactions as C-alkylation of acidic ketones and the acylation and sulfonylation of amines. First, we derive the following general equation for pHmax, the pH giving the highest yield of the product (P) of the reaction of a nucleophile (Nu) with a hydrolyzable electrophile (E) in water: pHmax = 1/2[log (kw/kOH) + PKw + pKw] (kw and kOH refer to the water- and hydroxide-promoted hydrolyses of E, Kw is the autoprotolysis constant of water, and Ka is the acid dissociation constant of NuH+, the conjugate acid of Nu). pHmax thus depends on a property of E (namely, kw/kOH) and a property of Nu (the pKa of NuH+), but not on the rate constant for the reaction of E with Nu or the concentration of Nu. We then deduce analogous approximate equations for maximum selectivity for reaction at either of two nucleophilic sites, specifically, equations giving pHxmax and pHymax, the pH values for the maximum yields of the respective products (Px and Py) of the reactions of E with the two nucleophiles. We find that (a) pH-yield profiles calculated from the equations concur with observed yields for reactions under pseudo-first-order conditions and (b) preparative experiments at the estimated pH values give good to excellent yields of clean products and high selectivity in both the C-alkylation and Schotten-Baumann reactions.

New Chiral Ligands designed for Palladium-catalysed Asymmetric Allylic Alkylation

New chiral phosphine ligands containing a chiral functional group remote from the phosphino-groups have been found to be effective in the palladium-catalysed reaction of allyl acetate with the enolate anion of 2-acetylcyclohexanone and give the allylated