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Upstream product

• 16520-62-0 4-Phenyl-1-butyne 
• 536-74-3 phenylacetylene 

Relevant academic research and scientific papers

Verkade Base in FLP Chemistry-From Stoichiometric C-H Bond Cleavage to the Catalytic Dimerization of Alkynes

Stoichiometric and catalytic reactions of terminal alkynes with various FLPs and Lewis acid-base adducts have been investigated. Reactions of phenylacetylene with FLPs composed of the Verkade base N[CH2CH2NPri]3

A Switchable Gold Catalyst by Encapsulation in a Self-Assembled Cage

Dinuclear gold complexes have the ability to interact with one or more substrates in a dual-activation mode, leading to different reactivity and selectivity than their mononuclear relatives. In this contribution, this difference was used to control the catalytic properties of a gold-based catalytic system by site-isolation of mononuclear gold complexes by selective encapsulation. The typical dual-activation mode is prohibited by this catalyst encapsulation, leading to typical behavior as a result of mononuclear activation. This strategy can be used as a switch (on/off) for a catalytic reaction and also permits reversible control over the product distribution during the course of a reaction.

Reaction Selectivity in On-Surface Chemistry by Surface Coverage Control—Alkyne Dimerization versus Alkyne Trimerization

This work reports the influence of molecular coverage in on-surface C?C-bond formation on reaction outcome. 6-Ethynyl-2-naphthoic acid (ENA) was chosen as organic component and Ag(111) as substrate. The alkyne moiety in ENA can either react by dimerizatio

Evaluation of the Reactivity of Metallocatalytic Cavities in the Dimerization of Terminal Alkynes

The effect of a metallocatalytic cavity flanked by aromatic rings on the catalytic dimerization of terminal alkynes was explored through a comparison with model catalysts that weakened the cavity. The diquinoxaline-spanned resorcin[4]arene provided a defi

An Introverted Bis-Au Cavitand and Its Catalytic Dimerization of Terminal Alkynes

A preparative synthesis of an inwardly oriented phosphoramidite-Au dinuclear resorcinarene cavitand complex is described, including a description of potent catalytic abilities. The cavitand structure was determined by crystallographic analysis, which revealed that the phosphoramidite P-N bonds point outside placing the two Au atoms inside. We explored the catalytic proclivity of the cavitand and found that it effeciently catalyzes selective and direct dimerization of terminal alkynes to afford conjugated enynes. Mixed dimerizations give rise to chemoselective products, and macrocyclization by intramolecular dimerization are both trademark capabilities of the method.

Evaluation of tuned phosphorus cavitands on catalytic cross-dimerization of terminal alkynes

Synthesis of four new bis-phosphorus cavitands is described, including a description of their catalytic use on cross-dimerization of terminal alkynes. The commercially available P[N(CH2CH3)2]3, PhP[N(CH2CH3)2]2, P(OCH3)3, and in situ generated P(NMeBn)3were reacted with a tetra-ol cavitand platform to provide new phosphorus ligands. These ligands readily formed bis-Au complexes that were examined to generate a reactivity profile for the catalytic cross-dimerization of terminal alkynes. We found that the ligand derived from P[N(CH3)2]3gave best product selectivity.

Gold-catalyzed regioselective dimerization of aliphatic terminal alkynes

A gold-catalyzed regioselective homodimerization of -aliphatic terminal alkynes is described. Bulky and less Lewis acidic t-BuXPhosAuNTf2 is the preferred catalyst, and the additive, anhydrous NaOAc, substantially facilitates the reaction. Geor

Enantioselective rhodium-catalyzed [2 + 2 + 2] cycloadditions of terminal alkynes and alkenyl isocyanates: Mechanistic insights lead to a unified model that rationalizes product selectivity

This manuscript describes the development and scope of the asymmetric rhodium-catalyzed [2 + 2 + 2] cycloaddition of terminal alkynes and alkenyl isocyanates leading to the formation of indolizidine and quinolizidine scaffolds. The use of phosphoramidite ligands proved crucial for avoiding competitive terminal alkyne dimerization. Both aliphatic and aromatic terminal alkynes participate well, with product selectivity a function of both the steric and electronic character of the alkyne. Manipulation of the phosphoramidite ligand leads to tuning of enantio- and product selectivity, with a complete turnover in product selectivity seen with aliphatic alkynes when moving from Taddol-based to biphenol-based phosphoramidites. Terminal and 1,1-disubstituted olefins are tolerated with nearly equal efficacy. Examination of a series of competition experiments in combination with analysis of reaction outcome shed considerable light on the operative catalytic cycle. Through a detailed study of a series of X-ray structures of rhodium(cod)chloride/phosphoramidite complexes, we have formulated a mechanistic hypothesis that rationalizes the observed product selectivity.