13312-96-4

Upstream product

• 769-68-6 2-phenylbutanenitrile 
• 1066-54-2 trimethylsilylacetylene 
• 59409-55-1 (1-ethyl-1,2-propadienyl)benzene 
• 19158-51-1 P-toluenesulfonyl cyanide 
• 212626-87-4 2-(2-bromophenyl)-2-ethylbutyronitrile 
• 19472-74-3 2-(2-bromophenyl)acetonitrile 

Downstream Products

• 5336-57-2 2-ethyl-2-phenyl-butyronitrile 
• 929685-30-3 4-cyano-4-phenyl-hexanoic acid [2-(3,4-dimethoxy-phenyl)-ethyl]-methyl-amide 
• 929685-27-8 4-cyano-4-phenyl-hexanoic acid [2-(3,4-dimethoxy-phenyl)-ethyl]-amide 

Relevant academic research and scientific papers

Mechanistic study of the selectivity of olefin versus cyclobutene formation by palladium(0)-catalyzed intramolecular C(sp3)-H activation

(Chemical Equation Presented) This study describes the mechanism and selectivity pattern of the Pd0-catalyzed C(sp3)-H activation of a prototypical substrate bearing two linear alkyl groups. Experimentally, the use of the Pd/P(t-Bu)3 catalytic system leads to a ca. 7:3 mixture of olefin and benzocyclobutene (BCB) products. The C-H activation step was computed to be favored for the secondary position α to the benzylic carbon over the primary position β to the benzylic carbon by more than 4 kcal mol-1, in line with previous selectivity trends on analogous substrates. The five-membered palladacycle obtained through this activation step may then follow two different pathways, which were computationally characterized: (1) decoordination of the protonated base and reductive elimination to give the BCB product and (2) proton transfer to the aryl ligand and base-mediated β-H elimination to give the olefin product. Experiments conducted with deuterated substrates were in accordance with this mechanism. The difference between the highest activation barriers in the two pathways was computed to be 1.2 kcal mol-1 in favor of BCB formation. However, the use of a kinetic model revealed the critical influence of the kinetics of dissociation of HCO3- formed after the C-H activation step in actually directing the reaction toward either of the two pathways.

Electrophilic cyanation of allylic boranes: Synthesis of β,γ-unsaturated nitriles containing allylic quaternary carbon centers

The electrophilic cyanation of allylic boranes, a process that is applicable to the construction of allylic quaternary carbon centers, is reported. The reaction has a broad substrate scope with a high functional group tolerance. The results represent an u

Palladium-catalyzed intramolecular C(sp3)-H functionalization: Catalyst development and synthetic applications

A novel catalytic system, based on a mixture of palladium acetate and tris(5-fluoro-2-methylphenyl)-phosphane (F-TOTP), has been designed for the intramolecular C-H functionalization of alkane segments. Among other analogues of tris(2-methylphenyl)phospha

Substituted benzocarbocycles by palladium-catalyzed cascade reactions featuring a C(sp3) - H activation step

Valuable 4- and 5-membered benzocarbocycles were synthesized via selective palladium-catalyzed cascade reactions which combined C(sp3)-H activation, Heck cyclization, Heck arylation or olefin hydrogenation. In all cases, all mechanistically independent steps were catalyzed by a single multi-functional catalyst.

The Palladium-Catalyzed C-H Activation of Benzylic gem-Dialkyl Groups

Palladacyclic intermediates effectively lower the high energy barrier to cleavage of a C(sp3)-H bond. C-H activation of benzylic gem-dialkyl groups of bromo- and iodobenzenes produces olefins and cyclobutabenzenes, respectively, without homocoupling (see scheme).

Cesium catalyzed addition of nitriles to alkynes

Benzylic cyanides add in the presence of a catalytic amount of cesium alkoxides in NMP inter- and intramolecularly to various acetylenes providing functionalized olefins with good regio- and stereoselectivities (E : Z ratios up to 99:1).