1647021-82-6

Basic information

• Product Name: dimethyl 3-(2-(p-methoxyphenyl)propan-2-yl)-4-vinylidenecyclopent-2-ene-1,1-dicarboxylate
• CAS NO: 1647021-82-6
• Molecular Weight: 356.419
• Mol File: 1647021-82-6.mol

Chemical Properties

• CAS DataBase Reference: dimethyl 3-(2-(p-methoxyphenyl)propan-2-yl)-4-vinylidenecyclopent-2-ene-1,1-dicarboxylate(CAS DataBase Reference)
• NIST Chemistry Reference: dimethyl 3-(2-(p-methoxyphenyl)propan-2-yl)-4-vinylidenecyclopent-2-ene-1,1-dicarboxylate(1647021-82-6)
• EPA Substance Registry System: dimethyl 3-(2-(p-methoxyphenyl)propan-2-yl)-4-vinylidenecyclopent-2-ene-1,1-dicarboxylate(1647021-82-6)

Safety Data

• Hazardous Substances Data: 1647021-82-6(Hazardous Substances Data)

Upstream product

• 1192068-12-4 dimethyl 2-(but-2-yn-1-yl)-2-(3-methylbuta-1,2-dien-1-yl)malonate 
• 7294-51-1 2,4,6-tris(4-methoxyphenyl)boroxine 
• 6214-32-0 1-bromo-3-methylbuta-1,2-diene 
• 5720-07-0 4-methoxyphenylboronic acid 

Relevant articles and documents

Kinetics and Mechanism of the Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes

Pd-catalyzed C-C bond-forming reactions under oxidative conditions constitute a class of important and widely used synthetic protocols. This Article describes a mechanistic investigation of the arylating carbocyclization of allenynes using boronic acids and focuses on the correlation between reaction conditions and product selectivity. Isotope effects confirm that either allenic or propargylic C-H activation occurs directly after substrate binding. With an excess of H2O, a triene product is selectively formed via allenic C-H activation. The latter C-H activation was found to be turnover-limiting and the reaction zeroth order in reactants as well as the oxidant. A dominant feature is continuous catalyst activation, which was shown to occur even in the absence of substrate. Smaller amounts of H2O lead to mixtures of triene and vinylallene products, where the latter is formed via propargylic C-H activation. The formation of triene occurs only in the presence of ArB(OH)2. Vinylallene, on the other hand, was shown to be formed by consumption of (ArBO)3 as a first-order reactant. Conditions with sub-stoichiometric BF3·OEt2 gave selectively the vinylallene product, and the reaction is first order in PhB(OH)2. Both C-H activation and transmetalation influence the reaction rate. However, with electron-deficient ArB(OH)2, C-H activation is turnover-limiting. It was difficult to establish the order of transmetalation vs C-H activation with certainty, but the results suggest that BF3·OEt2 promotes an early transmetalation. The catalytically active species were found to be dependent on the reaction conditions, and H2O is a crucial parameter in the control of selectivity.

Palladium-catalyzed oxidative arylating carbocyclization of allenynes: Control of selectivity and role of H2O

Highly selective protocols for the carbocyclization/arylation of allenynes using arylboronic acids are reported. Arylated vinylallenes are obtained with the use of BF3·Et2O as an additive, whereas addition of water leads to arylated trienes. These conditions provide the respective products with excellent selectivities (generally >97:3) for a range of boronic acids and different allenynes. It has been revealed that water plays a crucial role for the product distribution.