356784-34-4

Upstream product

• 108-05-4 vinyl acetate 
• 768-56-9 4-Phenylbut-1-ene 
• 75-24-1 trimethylaluminum 
• 80651-37-2 (R)-(-)-2-methyl-4-phenylbutyric acid 
• 16520-62-0 4-Phenyl-1-butyne 
• 128038-39-1 2-methylene-4-phenylbutanoic acid 
• 1191077-29-8 (R)-tert-butyl 2-methyl-4-phenylbutanoate 
• 40654-82-8 4-phenyl-2-methylbutanal 
• 100-42-5 styrene 
• 849436-05-1 (R)-2-methyl-4-phenylbutanal 
• 1378250-04-4 (E)-(3,6-dimethylhept-4-en-1-yl)benzene 
• 16939-57-4 (E)-buta-1,3-dienylbenzene 
• 31915-94-3 (Z)-1-Phenylbuta-1,3-diene 
• 1821-12-1 4-Phenylbutyric acid 

Downstream Products

• 1191077-27-6 (R)-(4-chloro-3-methylbutyl)benzene 
• 849436-05-1 (R)-2-methyl-4-phenylbutanal 

Relevant academic research and scientific papers

The asymmetric hydrogenation of 2-phenethylacrylic acid as the key step for the enantioselective synthesis of Citralis Nitrile

A catalytic approach to the enantioselective synthesis of Citralis Nitrile (3-methyl-5-phenyl-pentanenitrile, a citrus-type odorant) is described. The key step is the transition-metal catalyzed asymmetric hydrogenation of 2-phenethylacrylic aci

Copper-catalyzed allylic difluoromethylation of allyl carbonates with (difluoromethyl)zinc reagent

The catalytic allylic difluoromethylation of allyl carbonates with (difluoromethyl)zinc reagent, which can be readily prepared via iodine-zinc exchange reaction of difluoroiodomethane with diethylzinc, was achieved by employing copper salt as a catalyst.

Regio-, chemo-, and enantioselective Ni-catalyzed hydrocyanation of 1,3-dienes

A regio-, chemo-, and enantioselective nickel-catalyzed hydrocyanation of 1,3-dienes is reported. The key to the success of this asymmetric transformation is the use of a specific multichiral diphosphite ligand. In addition to aryl-substituted 1,3-dienes, highly challenging aliphatic 1,3-diene substrates can also be preferentially converted to the corresponding 1,2-adducts in decent yields with the highest enantioselectivities to date.

Application of Trimethylgermanyl-Substituted Bisphosphine Ligands with Enhanced Dispersion Interactions to Copper-Catalyzed Hydroboration of Disubstituted Alkenes

We report the incorporation of large substituents based on heavy main-group elements that are atypical in ligand architectures to enhance dispersion interactions and, thereby, enhance enantioselectivity. Specifically, we prepared the chiral biaryl bisphosphine ligand (TMG-SYNPHOS) containing 3,5-bis(trimethylgermanyl)phenyl groups on phosphorus and applied this ligand to the challenging problem of enantioselective hydrofunctionalization reactions of 1,1-disubtituted alkenes. Indeed, TMG-SYNPHOS forms a copper complex that catalyzes hydroboration of 1,1-disubtituted alkenes with high levels of enantioselectivity, even when the two substituents are both primary alkyl groups. In addition, copper catalysts bearing ligands possessing germanyl groups were much more active for hydroboration than one derived from DTBM-SEGPHOS, a ligand containing 3,5-di-tert-butyl groups and widely used for copper-catalyzed hydrofunctionalization. This observation led to the identification of DTMGM-SEGPHOS, a bisphosphine ligand bearing 3,5-bis(trimethylgermanyl)-4-methoxyphenyl groups as the substituents on the phosphorus, as a new ligand that forms a highly active catalyst for hydroboration of unactivated 1,2-disubstituted alkenes, a class of substrates that has not readily undergone copper-catalyzed hydroboration previously. Computational studies revealed that the enantioselectivity and catalytic efficiency of the germanyl-substituted ligands is higher than that of the silyl and tert-butyl-substituted analogues because of attractive dispersion interactions between the bulky trimethylgermanyl groups on the ancillary ligand and the alkene substrate and that Pauli repulsive interactions tended to decrease enantioselectivity.

Manganese-Catalyzed Stereospecific Hydroxymethylation of Alkyl Tosylates

The development of a stereospecific hydroxymethylation of alkyl tosylates using an inexpensive, first-row catalyst is described. The transformation proceeds under mild conditions with low pressure to deliver homologated alcohols as products. Chiral, nonracemic β-branched primary alcohols are obtained with high enantiospecificity from easily accessed secondary alkyl substrates. Simple modification of the reaction system also permits access to α-d2 alcohols. These studies use anionic metal carbonyl catalysis to access a synthetic equivalent of the challenging hydroxymethyl anion from carbon monoxide.

Enantioselective Copper-Catalyzed Methylboration of Alkenes

An enantioselective Cu-catalyzed borylative cross-coupling reaction of alkenes, bis(pinacolato)diboron (B2(pin)2), and methyl iodide is reported. Alkenes including styrenes, β-substituted styrenes, and challenging aliphatic olefins were smoothly transferred to the desired methylboration products with excellent diastereoselectivities (dr up to >99:1) and enantioselectivities (er up to 99:1). The utility of this process was demonstrated by the synthesis of naproxen and formal synthesis of two natural products.

Reversible 1,3-anti/syn-stereochemical courses in copper-catalyzed γ-selective allyl-alkyl coupling between chiral allylic phosphates and alkylboranes

The stereochemical courses of the copper-catalyzed allyl-alkyl coupling between enantioenriched chiral allylic phosphates and alkylboranes were switchable between 1,3-anti and 1,3-syn selectivities by the choice of solvents and achiral alkoxide bases with different steric demands. The reactions with γ-silylated allylic phosphates allow efficient synthesis of enantioenriched chiral allylsilanes with tertiary or quaternary carbon stereogenic centers. Cyclic and acyclic bimodal participation of alkoxyborane species in an organocopper addition-elimination sequence is proposed to account for the phenomenon of the anti/syn-stereochemical reversal.

Identification of a valuable kinetic process in copper-catalyzed asymmetric allylic alkylation

Copper bottomed: The application of a previously described process of dynamic kinetic asymmetric transformation to acyclic substrates allowed the identification of a relevant kinetic process in the title reaction (see scheme; CuTC= copper(I) thiophencarboxylate, Naphth= naphthyl). The optimization of the reaction conditions and generality of the method, as well as mechanistic considerations are disclosed.

Iterative synthesis of (Oligo)deoxypropionates via zinc-catalyzed enantiospecific sp3-sp3cross-coupling

This group's recently reported mild zinc-catalyzed enantlospeclflc sp 3-sp3 cross-coupling of lactic acid tert-butylester triflate with Grignard reagents was now applied to an iterative approach in the synthesis of a series of all fo

Zirconium-catalyzed asymmetric carboalumination of alkenes: ZACA-lipase-catalyzed acetylation synergy

ZACA-lipase-catalyzed acetylation tandem reactions provide highly efficient and selective routes to either (R)- or (S)-2-methyl-1-alkanols, making, for the first time, the ZACA-based asymmetric synthesis of 2-methyl-1-alkanols widely applicable and satisfactory.