94922-12-0

Upstream product

• 101268-55-7 4,4-bis(ethoxycarbonyl)-1-hepten-6-yne 
• 67-56-1 methanol 
• 201230-82-2 carbon monoxide 
• 118453-14-8 diethyl 2-(2-bromo-2-propenyl)-2-(2-propenyl)propanedioate 
• 2049-80-1 (2-propenyl)propanedioic acid diethyl ester 

Relevant academic research and scientific papers

Palladium catalysed cyclisation-carbonylation of enynes to give cyclic γ,δ-unsaturated acids

In the presence of acetic acid, trifurylphosphine and CO (2 atm), palladium catalyses the conversion of a range of enynes to cyclic δ,γ-unsaturated carboxylic acids in good yield.

Synthesis of monoalkoxide monopyrrolyl complexes Mo(NR)(CHR′) (OR″)(pyrrolyl): Enyne metathesis with high oxidation state catalysts

Addition of 1 equiv of ROH to Mo(NAr)(CHCMe2Ph)(Me2Pyr)2 (Ar = 2,6-i-Pr2C6H3, Me2Pyr = 2,5-dimethylpyrrolyl) in diethyl ether or THF yields Mo(NAr)(CHCMe2Ph)(OR)(Mesu

Ligand-enforced intimacy between a gold cation and a carbenium ion: impact on stability and reactivity

Controlling the reactivity of transition metal complexes by positioning non-innocent functionalities around the catalytic pocket is a concept that has led to significant advances in catalysis. Here we describe our efforts toward the synthesis of dicationi

Pentiptycene-based concave NHC-metal complexes

The reaction of 1-amino,4-hydroxy-pentiptycene with diacetyl or acenaphthene-1,2-dione gave the respective diimines, followed by alkylation of the hydroxyl groups, and cyclization of the alkylated diimines to the respective bispentiptycene-imidazolium sal

Highly β-Selective Cyclopolymerization of 1,6-Heptadiynes and Ring-Closing Enyne Metathesis Reaction Using Grubbs Z-Selective Catalyst: Unprecedented Regioselectivity for Ru-Based Catalysts

It is well-known that Ru-based Grubbs catalysts undergo a highly selective α-addition to alkynes to promote exo-cyclization during ring-closing enyne metathesis (RCEYM) or to produce conjugated polyenes containing five-membered rings during the cyclopolymerization (CP) of 1,6-heptadiynes. There are a few reports of β-selective addition to alkynes using Schrock catalysts based on Mo but none for readily accessible and easy-to-use Ru-based catalysts. We report the first example of β-selective addition to alkynes using Grubbs Z-selective catalyst, which produces only endo products during the RCEYM reaction of terminal enynes and promotes the CP of 1,6-heptadiyne derivatives to give conjugated polyenes containing a six-membered ring as a major repeat unit. This unique preference for β-selectivity originated from the side-bound approach of alkynes to the catalyst, where the steric hindrance between the chelating N-heterocyclic carbene ligand of the catalyst and the alkynes disfavored α-addition. To enhance the β-selectivity for CP further, one could increase the size of the substrates on the monomers and lower the reaction temperature to obtain conjugated polyenes containing up to 95% six-membered rings. Moreover, the physical properties of the resulting polymer were analyzed in detail and compared with those of the conjugated polyenes containing only five-membered rings prepared from the same monomer but with a conventional Grubbs catalyst.

Gold phosphole complexes as efficient catalysts for alkyne activation

Gold(I) complexes bearing monophosphole ligands were synthesized, and their electronic and steric properties were compared to those of their triphenylphosphine-based counterparts. Cationic phosphole-based gold(I) complexes are active and selective in enyne cycloisomerization and in olefin cyclopropanation, with a good correlation between the ligand σ-donor ability and the catalytic activity. For the most efficient ligand, 1-phenyl-2,3,4,5-tetramethylphosphole (TMP), a highly active, selective, and stable cationic [Au(TMP)(CH3CN)]SbF6 complex was isolated.

Endo-selective enyne ring-closing metathesis promoted by stereogenic-at-Mo monoalkoxide and monoaryloxide complexes. Efficient synthesis of cyclic dienes not accessible through reactions with Ru carbenes

Stereogenic-at-Mo monoalkoxide and monoaryloxide complexes promote enyne ring-closing metathesis (RCM) reactions, affording the corresponding endo products with high selectivity (typically >98: 2 endo:exo). All catalysts can be prepared and used in situ.

Skeletal reorganization of enynes catalyzed by InCl3

The skeletal reorganization of enynes is achieved by the presence of InCl3 as the catalyst. The reaction of enynes having a terminal acetylenic moiety proceeds in a stereospecific manner to give 1-vinylcycloalkenes. The reaction of enynes conta

Palladium-catalyzed cycloalkylations of 2-bromo-l,n-dienes with organoboronic acids

Cascade palladium-catalyzed cycloalkylations of 2-bromo-1,n-dienes were accomplished in good to excellent yields, where the alkylpalladium intermediates, formed via an intramolecular Heck reaction of 2-bromo-1,n-dienes (n = 6 or 7), were successfully cros

Effects of Olefin Substitution on the Ring-Closing Metathesis of Dienes

Ruthenium alkylidene 1 and molybdenum alkylidene 2 have been utilized in the ring-closing metathesis (RCM) of dienes containing gem-disubstituted olefins to yield tri- and tetrasubstituted cyclic olefins. Dienes with sterically demanding and/or electron-withdrawing substituents such as Ph, CO2Me, and tBu were cyclized successfully with 2, but did not cyclize with 1. Tetrasubstituted cyclic olefins could be formed with 2, but not using alkylidene 1. Dienes with allylic functional groups yielded functionalized cyclic olefins when treated with 1.