29800-82-6

Upstream product

• 2039-85-2 3-Chlorostyrene 
• 587-04-2 m-Chlorobenzaldehyde 
• 50-00-0 formaldehyd 
• 766-83-6 m-chlorophenylacetylene 
• 127510-49-0 1-chloro-3-(2,2-dibromocyclopropyl)benzene 

Downstream Products

• 1402235-33-9 2-(3-(3-chlorophenyl)prop-1-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 1397283-37-2 (Z)-2-(1-(m-chlorophenyl)prop-1-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 

Relevant academic research and scientific papers

Photoredox Catalyzed Sulfonylation of Multisubstituted Allenes with Ru(bpy)3Cl2 or Rhodamine B

A highly regio- and stereoselective sulfonylation of allenes was developed that provided direct access to α, β-substituted unsaturated sulfone. By means of visible-light photoredox catalysis, the free radicals produced by p-toluenesulfonic acid reacted with multisubstituted allenes to obtain Markovnikov-type vinyl sulfones with Ru(bpy)3Cl2 or Rhodamine B as photocatalyst. The yield of this reaction could reach up to 91%. A series of unsaturated sulfones would be used for further transformation to some valuable compounds.

Copper(ii)-catalyzed protoboration of allenes in aqueous media and open air

A method has been developed for the facile Cu(ii)-catalyzed protoboration of monosubstituted allenes in aqueous media under atmospheric conditions. The reaction occurs site selectively, favoring internal alkene protoboration to afford 1,1-disubstituted vinylboronic acid derivatives (up to 93?:?7) with modest to good yields. The method has been applied to a variety of phenylallene derivatives as well as alkyl-substituted allenes. This journal is

Photoredox-Catalyzed α-Aminoalkylcarboxylation of Allenes with CO2

The photoredox-catalyzed α-aminoalkylcarboxylation of aryl allenes with CO2 and N,N-dimethylanilines is reported for the first time (26 examples, up to 96% yield). In the case of electron-deficient allenes, good regioselectivity was observed (up to 94:6), exclusively generating kinetic products over thermodynamic products. This protocol is a novel synthetic method for highly functionalized β,γ-unsaturated γ-aminobutyric esters.

Palladium-Catalyzed Oxidative Carbonylative Coupling of Arylallenes, Arylboronic Acids, and Nitroarenes

In this Letter, a palladium-catalyzed multicomponent procedure for the selective synthesis of α-substituted α,β-unsaturated ketones has been developed. With readily available allenes, arylboronic acids, and nitroarenes as the substrates, the reaction proceeds selectively to the desired α-substituted enones. Notably, no manipulation of carbon monoxide gas is needed here, and Mo(CO)6 has been applied as a stable solid CO source instead. Additionally, as an oxidative coupling reaction, nitroarenes are used as both the amine source and the oxidant to regenerate the active palladium species.

Chlorination of phenylallene derivatives with 1-chloro-1,2-benziodoxol-3-one: Synthesis of vicinal-dichlorides and chlorodienes

Allyl and vinyl chlorides represent important structural motifs in organic chemistry. Herein is described the chemoselective and regioselective reaction of aryl- and α-substituted phenylallenes with the hypervalent iodine (HVI) reagent 1-chloro-1,2-benz-iodoxol-3-one. The reaction typically results in vicinal dichlorides, except with proton-containing α-alkyl substituents, which instead give chlorinated dienes as the major product. Experimental evidence suggests that a radical mechanism is involved.

Copper-Catalyzed Difunctionalization of Allenes with Sulfonyl Iodides Leading to (E)-α-Iodomethyl Vinylsulfones

A highly regioselective iodosulfonylation of allenes in the presence of CuI and 1,10-phenanthroline has been developed for the synthesis of various useful (E)-α-iodomethyl vinylsulfones in moderate to excellent yields. This practical reaction is fast, operationally simple, and in particular, proceeds under very mild conditions to afford the target products with high regio- and stereoselectivity. The selectivity was illustrated by a conceptual DFT analysis.

Fluorinative Rearrangements of Substituted Phenylallenes Mediated by (Difluoroiodo)toluene: Synthesis of α-(Difluoromethyl)styrenes

Phenylallenes undergo fluorinative rearrangement upon the action of (difluoroiodo)toluene in the presence of 20 mol % BF3?OEt2 to yield α-difluoromethyl styrenes. This unprecedented reaction was entirely chemoselective for the internal allene π bond, and showed remarkable regioselectivity during the fluorination event. Substituted phenylallenes, phenylallenes possessing both phenyl- and α-allenyl substituents, and diphenylallenes were investigated, and good functional-group compatibility was observed throughout. The ease with which allenes can be prepared on a large scale, and the operational simplicity of this reaction allowed us to rapidly access fluorine-containing building blocks that have not been accessed by conventional deoxyfluorination strategies.

Highly Regio- and Enantioselective Alkoxycarbonylative Amination of Terminal Allenes Catalyzed by a Spiroketal-Based Diphosphine/Pd(II) Complex

An enantioselective alkoxycarbonylation-amination cascade process of terminal allenes with CO, methanol, and arylamines has been developed. It proceeds under mild conditions (room temperature, ambient pressure CO) via oxidative Pd(II) catalysis using an aromatic spiroketal-based diphosphine (SKP) as a chiral ligand and a Cu(II) salt as an oxidant and affords a wide range of α-methylene-β-arylamino acid esters (36 examples) in good yields with excellent enantioselectivity (up to 96% ee) and high regioselectivity (branched/linear > 92:8). Preliminary mechanistic studies suggested that the reaction is likely to proceed through alkoxycarbonylpalladation of the allene followed by an amination process. The synthetic utility of the protocol is showcased in the asymmetric construction of a cycloheptene-fused chiral β-lactam.

Cu(I)-NHC-Catalyzed Silylation of Allenes: Diastereoselective Three-Component Coupling with Aldehydes

Copper-catalyzed silylation of aryl allenes using a silylborane reagent affords vinyl silane building blocks with high efficiency. The use of a seven-membered NHC ligand proved crucial for high regioselectivity. The catalytically generated allylcoppper intermediates were intercepted by aldehydes in a diastereoselective three-component coupling to furnish homoallylic alcohols. Seven′s up! The use of a seven-membered N-heterocyclic carbene (NHC) ligand proved crucial in exerting high regiocontrol during the development of the first copper-catalyzed silylation of allenes using a commercial silylborane reagent. The process affords privileged vinyl silane building blocks with high efficiency. Allylcopper intermediates can be intercepted by aldehydes in a highly diastereoselective three-component coupling to furnish homoallylic alcohols.

Some reactions of gem-dibromocyclopropanes and metal carbonyls

A series of gem-dibromocyclopropanes were treated with various metal complexes. Among the metal complexes, Ru(CO)2(PPh3) 3, Ru(CO)3(PPh3)2, and Mo(CO) 6 were able to remove a bro