42443-38-9

Upstream product

• 591-50-4 iodobenzene 
• 917-54-4 methyllithium 
• 4891-38-7 phenylpropynoic acid methyl ester 
• 67-56-1 methanol 
• 201230-82-2 carbon monoxide 
• 59176-55-5 ethyl α,α-dibromobenzeneacetate 
• 98-86-2 acetophenone 
• 74-88-4 methyl iodide 
• 98-80-6 phenylboronic acid 
• 16648-44-5 methyl α-acetylphenylacetate 
• 101-41-7 benzeneacetic acid methyl ester 
• 15206-55-0 methyl 2-oxo-2-phenylacetate 
• 532-28-5 (RS)-mandelonitrile 
• 100-52-7 benzaldehyde 

Downstream Products

• 34317-82-3 2,3-diphenyl-crotonic acid 

Relevant academic research and scientific papers

Stereospecific Electrophilic Fluorocyclization of α,β-Unsaturated Amides with Selectfluor

An efficient fluorocyclization of α,β-unsaturated amides through a formal halocyclization process is developed. The reaction proceeds under transition-metal-free conditions and leads to the formation of fluorinated oxazolidine-2,4-diones with excellent regio- and diastereoselectivity. The evaluation of the reaction mechanism based on preliminary experiments and density functional theory calculations suggests that a synergetic syn-oxo-fluorination occurs and is followed by an anti-oxo substitution reaction. The reaction opens a new window in the field of stereospecific fluorofunctionalization.

Stereoretentive suzuki-miyaura and kumada-Tamao-corriu cross-couplings for preparing (E)-and (Z)-stereodefined, fully substituted α,β-unsaturated esters: Application for a pharmacophore synthesis

Substrate-general stereocomplementary Suzuki-Miyaura (SM) cross-coupling and relevant Kumada-Tamao-Corriu (KTC) crosscoupling reactions for preparing (E)-and (Z)-stereodefined, fully substituted α,β-unsaturated esters are described. The SM cross-coupling

Divergent Synthetic Access to E- and Z-Stereodefined All-Carbon-Substituted Olefin Scaffolds: Application to Parallel Synthesis of (E)- and (Z)-Tamoxifens

A highly substrate-general synthesis of all-carbon-substituted E- and Z-stereodefined olefins is performed. The method comprises two sets of parallel and stereocomplementary preparations of (E)- and (Z)-α,β-unsaturated esters involving two robust and distinctive reactions: 1) stereocomplementary enol tosylations using readily available TsCl/diamine/(LiCl) base reagents, and 2) stereoretentive Negishi cross-coupling using the catalysts [Pd(dppe)Cl2] (for E) and [Pd(dppb)Cl2] (for Z). The present parallel approach is categorized as both type I (convergent approach: 16 examples, 56–87 % yield) and type II (divergent approach: 18 examples, 70–95 % yield). The obtained (E)- and (Z)-α,β-unsaturated ester scaffolds are successfully transformed into various E- and Z-stereodefined known and novel olefins (8×2 derivatization arrays). As a demonstration, application to the parallel synthesis of both (E)- and (Z)-tamoxifens, a representative motif of all-carbon-substituted olefins, is accomplished in a total of eight steps with an overall yield of 58 % (average 93 %) and 57 % (average 93 %), respectively.

(E)- and (Z)-stereodefined enol phosphonates derived from β-ketoesters: Stereocomplementary synthesis of fully-substituted α,β-unsaturated esters

A versatile, robust, and stereocomplementary synthesis of fully-substituted (E)- and (Z)-stereodefined α,β-unsaturated esters 3 from accessible α-substituted β-ketoesters 1via (E)- and (Z)-enol phosphonates was achieved. The present method involves two ac

P(NMe2)3-Mediated Umpolung Alkylation and Nonylidic Olefination of α-Keto Esters

A commercial phosphorus-based reagent (P(NMe2)3) mediates umpolung alkylation of methyl aroylformates with benzylic and allylic bromides, leading to either Barbier-type addition or ylide-free olefination products upon workup. The reaction sequence is initiated by a two-electron redox addition of the tricoordinate phosphorus reagent with an α-keto ester compound (Kukhtin-Ramirez addition). A mechanistic rationale is offered for the chemoselectivity upon which the success of this nonmetal mediated C-C bond forming strategy is based.

(E)-,(Z)-parallel preparative methods for stereodefined β,β-diaryl- and α,β-diaryl-α,β-unsaturated esters: Application to the stereocomplementary concise synthesis of zimelidine

Parallel and practical methods for the preparation of both (E)- and (Z)-β-aryl1-β-aryl2-α,β-unsaturated esters 1 and (E)- and (Z)-α-aryl1-β-aryl2-α,β-unsaturated esters 2 are described. These methods involve accessible, robust, stereocomplementary N-methylimidazole (NMI)-mediated enol tosylations (14 examples, 70-99 % yield), as well as stereoretentive Suzuki-Miyaura cross-couplings (36 examples, 64-99 % yield). The highlighted feature of the present protocol is the use of parallel and stereocomplementary approaches to obtain highly (E)- and (Z)-pure products 1 and 2 by utilizing sequential enol tosylations and cross-coupling reactions. An expeditious and parallel synthesis of (E)- and (Z)-zimelidine (3), which is a highly representative selective serotonin reuptake inhibitor (SSRI), was performed by utilizing the present methods.

Stereoselective olefination of unfunctionalized ketones via ynolates

Ynolates react with ketones at room temperature to afford α,β,β,-trisubstituted acrylates (tetra-substituted olefins) with 2:1-8:1 geometrical selectivities. This can be regarded as a new olefination reaction of ketones giving tetrasubstituted olefins in good yield, even in the case of sterically hindered substrates. The reaction mechanism involves cycloaddition of ynolates with a carbonyl group and subsequent thermal electrocyclic ring-opening of the resulting β-lactone enolates. The stereoselectivity is determined in the ring-opening, which is regulated by torquoselectivity. In this paper, we describe the scope and limitations of olefination of ketones via ynolates and discuss the stereocontrol mechanism.

Photochemical Wittig Reaction of Quasi-phosphonium Ylides

α-(Methoxycarbonyl)benzylidene quasi-phosphonium ylides, which are unreactive towards most carbonyl compounds, are found to undergo the Wittig reaction upon irradiation; irradiation with acyclic carbonyl compounds, e.g. benzaldehydes and acetophenones, af

Palladium(0)-Catalyzed Coupling Reaction of Lithium (α-Carbalkoxyvinyl)cuprates with Organic Halides

The palladium(0)-catalyzed coupling reaction of lithium (α-carbalkoxyvinyl)(dicyclohexylamido)cuprates and organic halides such as aryl, vinyl, and benzyl halides was investigated.The lithium (α-carbalkoxyvinyl)dicyclohexylamido)cuprates were generated by conjugate addition of organo(dicyclohexylamido)cuprates to α,β-acetylenic esters.The coupling reaction using a Pd(PPh3)4 catalyst proceeded at room temperature to give synthetically useful α,β-substituted acrylates in good yields.The coupling reaction of the (α-carbalkoxyvinyl)(dicyclohexylamido)cuprate derived from a β-unsubstituted α,β-acetylenic ester took place stereoselectively to give an (E)-α,β-substituted acrylate derivative.In the vinyl halide reaction, the stereochemistry of the vinyl halide component is retained in the coupling product.The use of the dicyclohexylamido group as a nontransferable ligand is important.Thus, in the reaction using an (α-carbalkoxyvinyl)(1-hexynyl)cuprate complex, a nonselective coupling involving the 1-hexynyl group took place.

Mechanism, regiochemistry, and stereochemistry of the insertion reaction of alkynes with methyl(2,4-pentanedionato)(triphenylphosphine)nickel. A cis insertion that leads to trans kinetic products

This study reports the rapid reaction under mild conditions of internal and terminal alkynes with methyl(2,4-pentanedionato)(triphenylphosphine)nickel (1) in aromatic and ethereal solvents. In all cases vinylnickel products (2) are formed by insertion of the alkyne into the nickel-methyl bond. The regiochemistry is unusual; unsymmetrical alkynes give selectively the one regioisomer with the sterically largest substituent next to the nickel atom. So that the stereochemistry of the initial insertion could be investigated, an X-ray diffraction study of the reaction of 1 and diphenylacetylene was carried out. This showed that the vinylnickel complex formed by overall trans insertion was the product of the reaction. Furthermore, subsequent slow isomerization of this complex, to a mixture of it and the corresponding cis isomer, demonstrated that this trans addition product is the kinetic product of the reaction. In studies with other alkynes, the product of trans addition was not always exclusively (or even predominantly) formed, but the ratio of the stereoisomers formed kinetically was substantially different from the thermodynamic ratio. Isotope labeling, added phosphine, and other experiments have allowed us to conclude that the mechanism of this reaction does involve cis addition. However, a coordinatively unsaturated vinylnickel intermediate is initially formed, which can undergo rapid, phosphine-catalyzed cis-trans isomerization in competition with its conversion to the isolable phosphine-substituted products.