77134-01-1

Upstream product

• 37559-18-5 3-phenylprop-2-ynyl acetate 
• 591-87-7 Allyl acetate 
• 62-38-4 phenylmercuric acetate 
• 67-56-1 methanol 
• 21040-45-9 Cinnamyl acetate 
• 4510-34-3 (Z)-cinnamyl alcohol 
• 108-24-7 acetic anhydride 
• 1504-58-1 3-Phenyl-2-propyn-1-ol 
• 300-57-2 allylbenzene 
• 64-19-7 acetic acid 
• 19713-73-6 methyl (2Z)-3-phenylprop-2-enoate 
• 103-54-8 cinnamyl acetate 
• 100-42-5 styrene 
• 25260-60-0 cis-1,4-bis(acetyloxy)but-2-ene 

Downstream Products

• 21040-45-9 Cinnamyl acetate 
• 63082-55-3 diethyl (E)-cinnamyl malonate 
• 72335-26-3 Ethyl-(1-phenyl)-allylmalonat 
• 59277-52-0 (Z)-3-(ethylthio)-1-phenylpropene 
• 3412-44-0 (1E)-1,3-diphenylpropene 
• 5882-82-6 (E)-1-(3-phenylallyl)piperidine 
• 1223575-17-4 (Z)-1-chloro-4-(3-phenyl-allylsulfanyl)benzene 
• 1223575-25-4 (Z)-(3-dodecylsulfanyl-propenyl)-benzene 
• 1223575-24-3 (E)-(3-dodecylsulfanyl-propenyl)-benzene 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 22665-13-0 1-phenylallyl methyl ether 
• 4510-34-3 (Z)-cinnamyl alcohol 
• 7217-71-2 1-phenyl-2-propenyl acetate 
• 876309-34-1 (Z)-3-(4-methoxyphenoxy)-1-phenylpropene 

Relevant academic research and scientific papers

Synthesis of a polyisobutylene-tagged fac-Ir(ppy)3 complex and its application as recyclable visible-light photocatalyst in a continuous flow process

The facile synthesis and application of a polyisobutylene-polymer-tagged, iridium(iii) photocatalyst is described. The catalytic performance of this complex remains consistently high, while the installed tether allows for its convenient separation from reaction products through a thermomorphic solvent system. Excellent recycling properties were observed both in batch and in flow reactions, and especially in the latter the continuous, automatic recovery and reuse of the catalyst either from a mono- or a biphasic reaction solution is realised, making this approach attractive for large-scale applications.

Influence of the N→Ru Coordinate Bond Length on the Activity of New Types of Hoveyda-Grubbs Olefin Metathesis Catalysts Containing a Six-Membered Chelate Ring Possessing a Ruthenium-Nitrogen Bond

An efficient approach to the synthesis of new types of Hoveyda-Grubbs catalysts containing an N→Ru bond in a six-membered chelate ring is proposed. The synthesis of the organometallic compounds is based on the interaction of ready accessible 2-vinylbenzylamines and 1,3-bis(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine ligands with dichloro(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphane)ruthenate, and it afforded the target ruthenium complexes in 70-80% yields. Areas of practical utility and potential applications of the obtained chelates were highlighted by tests of the catalysts in different olefin cross-metathesis (CM) and ring-closing-metathesis (RCM) reactions. These experiments revealed a high catalytic performance (up to 10-2 mol %) of all the synthesized structures in a broad temperature range. The structural peculiarities of the resultant ruthenium catalysts were thoroughly investigated by X-ray crystallography, which allowed making a reliable correlation between the structure of the metallo-complexes and their catalytic properties. It was proved that the bond length between ruthenium and nitrogen in the six-membered chelate ring has the greatest effect on the stability and efficiency of the catalyst. As a rule, the shorter and stronger the N→Ru bond, the higher the stability of the complex and the worse its catalytic characteristics. In turn, the coordination N→Ru bond length can be finely tuned and varied over a wide range of values by changing the steric volume of the cyclic substituents at the nitrogen atom, which will make it possible, as appropriate, to obtain in the future metal complexes with predictable stability and the required catalytic activity. Also, it was found that complexes in which the nitrogen atom is included in the morpholine or isoquinoline rings are the most efficient catalysts in this series. An attempt to establish a correlation between the N→Ru bond length and the 1H and 13C chemical shifts in the Ru═CH fragment has been made.

Photocatalyzed Diastereoselective Isomerization of Cinnamyl Chlorides to Cyclopropanes

Endergonic isomerizations are thermodynamically unfavored processes that are difficult to realize under thermal conditions. We report a photocatalytic and diastereoselective isomerization of acyclic cinnamyl chlorides to strained cyclopropanes. Quantum mechanical calculations (uM06-2X and DLPNO), including TD-DFT calculations, and experimental studies provide evidence for the energy transfer from an iridium photocatalyst to the allylic chloride substrate followed by C-Cl homolytic cleavage. Subsequent Cla￠ radical migration forms a localized triplet 1,3-diradical intermediate that, after intersystem crossing, undergoes ring-closing to form the desired product. The mild reaction conditions are compatible with a broad range of functional groups to generate chlorocyclopropanes in high yields and diastereoselectivities. A more efficient process is developed by addition of a catalytic amount of a nickel complex, and we propose a novel role for this cocatalyst to recycle an allyl chloride byproduct generated in the course of the reaction. The reaction is also shown to be stereoconvergent, as an E/Z mixture of cinnamyl chlorides furnish the anti-chlorocyclopropane product in high diastereoselectivity. We anticipate that the use of a visible light activated photocatalyst to transform substrates in combination with a transition metal catalyst to recycle byproducts back into the catalytic cycle will provide unique opportunities for the discovery of new reactivity.

Aerobic Acyloxylation of Allylic C?H Bonds Initiated by a Pd0 Precatalyst with 4,5-Diazafluoren-9-one as an Ancillary Ligand

Palladium-catalyzed allylic C?H oxidation has been widely studied, but most precedents use acetic acid as the coupling partner. In this study, a method compatible with diverse carboxylic acid partners has been developed. Use of a Pd0 precatalyst under aerobic reaction conditions leads to oxidation of Pd0 by O2 in the presence of the desired carboxylic acid to generate a PdII dicarboxylate that promotes acyloxylation of the allylic C?H bond. Good-to-excellent yields are obtained with a roughly 1:1 ratio of the alkene and carboxylic acid reagents. Optimized reaction conditions employ 4,5-diazafluoren-9-one (DAF) as a ligand, in combination with a quinone/iron phthalocyanine cocatalyst system to support aerobic catalytic turnover.

Stereodivergent Alkyne Reduction by using Water as the Hydrogen Source

A homogeneous Pd-catalyzed stereodivergent reduction of alkynes to Z and E alkenes by using H2O as the H2 source is presented. Mediated by a diboron reagent, the transfer hydrogenation has been accomplished to yield the desired geometrical isomer by rational ligand selection. The switchable stereoselectivity achieved using simple phosphine ligands is generally excellent. D2O has also been used as a D2 source for synthesizing the corresponding deuterated olefins. Supported by a gram-scale synthesis, the reaction can easily be scaled up making it an efficient way to prepare alkenes commercially as well. Mechanistic studies suggest formation of H?PdL2?OAc as the crucial step leading to the presence of two pathways involving H?Pd?B(OR)2 and molecular H2 as active intermediates.

S,O-ligand-promoted palladium-catalyzed C–H olefination of arenes with allylic substrates

An efficient catalytic system for the C–H olefination of arenes with different allylic substrates is reported. The catalytic system is based on Pd(OAc)2 and a readily accessible bidentate S,O-ligand. The methodology shows high activity with a wide range of arenes, including bulky and, electron-rich and -poor arenes. The applicability of this catalyst is demonstrated in the late-stage functionalization of the complex molecule O-methylestrone.

Stereoselective and Site-Specific Allylic Alkylation of Amino Acids and Small Peptides via a Pd/Cu Dual Catalysis

We report a stereoselective and site-specific allylic alkylation of Schiff base activated amino acids and small peptides via a Pd/Cu dual catalysis. A range of noncoded α,α-dialkyl α-amino acids were easily synthesized in high yields and with excellent enantioselectivities (up to >99% ee). Furthermore, a direct and highly stereoselective synthesis of small peptides with enantiopure α-alkyl or α,α-dialkyl α-amino acids residues incorporated at specific sites was accomplished using this dual catalyst system.

Evaluating the thermal vinylcyclopropane rearrangement (VCPR) as a practical method for the synthesis of difluorinated cyclopentenes: Experimental and computational studies of rearrangement stereospecificity

Vinyl cyclopropane rearrangement (VCPR) has been utilised to synthesise a difluorinated cyclopentene stereospecifically and under mild thermal conditions. Difluorocyclopropanation chemistry afforded ethyl 3-(1'(2'2'-difluoro-3'-phenyl)cyclopropyl) propenoate as all four stereoisomers (18a, 18b, 22a, 22b) (all racemic). The trans-E isomer (18a), prepared in 70% yield over three steps, underwent near quantitative VCPR to difluorocyclopentene 23 (99 %). Rearrangements were monitored by 19F NMR (100-180 °C). While cis/trans cyclopropane stereoisomerisation was facile, favouring trans-isomers by a modest margin, no E/Z alkene isomerisation was observed even at higher temperatures. Neither cis nor trans Z-alkenoates underwent VCPR, even up to much higher temperatures (180 °C). The cis-cyclopropanes underwent [3,3]-rearrangement to afford benzocycloheptadiene species. The reaction stereospecificity was explored by using electronic structure calculations, and UB3LYP/6-31G methodology allowed the energy barriers for cyclopropane stereoisomerisation, diastereoisomeric VCPR and [3,3]-rearrangement to be ranked in agreement with experiment.

Facile synthesis of Z -alkenes via uphill catalysis

Catalytic access to thermodynamically less stable Z-alkenes has recently received considerable attention. These approaches have relied upon kinetic control of the reaction to arrive at the thermodynamically less stable geometrical isomer. Herein, we present an orthogonal approach which proceeds via photochemically catalyzed isomerization of the thermodynamic E-alkene to the less stable Z-isomer which occurs via a photochemical pumping mechanism. We consider two potential mechanisms. Importantly, the reaction conditions are mild, tolerant, and operationally simple and will be easily implemented.

Allylic C-H acetoxylation with a 4,5-diazafluorenone-ligated palladium catalyst: A ligand-based strategy to achieve aerobic catalytic turnover

Pd-catalyzed C-H oxidation reactions often require the use of oxidants other than O2. Here we demonstrate a ligand-based strategy to replace benzoquinone with O2 as the stoichiometric oxidant in Pd-catalyzed allylic C-H acetoxylation. Use of 4,5-diazafluorenone (1) as an ancillary ligand for Pd(OAc)2 enables terminal alkenes to be converted to linear allylic acetoxylation products in good yields and selectivity under 1 atm O 2. Mechanistic studies have revealed that 1 facilitates C-O reductive elimination from a π-allyl-PdII intermediate, thereby eliminating the requirement for benzoquinone in this key catalytic step.