16917-32-1

Upstream product

• 5293-84-5 chloromethyltriphenylphosphonium chloride 
• 98-86-2 acetophenone 
• 592-41-6 1-hexene 
• 91309-64-7 3-Chloro-3-(1-phenyl-ethyl)-3H-diazirine 
• 691-38-3 (Z)-4-methyl-2-pentene 
• 1455-13-6 deuteromethanol 
• 3360-53-0 1-bromo-2-phenyl-1-propene 
• 704-80-3 (E)-3-phenyl-2-butenoic acid 
• 98-83-9 isopropenylbenzene 
• 66775-59-5 (E)-(2-phenyl-1-propenyl)dimethylalane 
• 536-74-3 phenylacetylene 
• 911803-13-9 1-bromo-1-chloro-2-hydroxy-prop-2-yl-benzene 
• 209391-68-4 (E)-1-[(1-chloro-2-phenylprop-1-en-1-yl)sulfinyl]-4-methylbenzene 
• 88211-06-7 α-methylbenzylchlorocarbene 

Downstream Products

• 66279-61-6 trans-3-Phenyl-2-chlor-3-methyl-acrylsaeure 
• 117582-80-6 (E)-(1-cyclohexylprop-1-en-2-yl)benzene 
• 74866-37-8 [3-(benzenesulfonyl)prop-1-en-2-yl]benzene 
• 779-51-1 cis-α-methylstilbene 

Relevant academic research and scientific papers

Iron-Catalyzed Cross-Coupling of Alkynyl and Styrenyl Chlorides with Alkyl Grignard Reagents in Batch and Flow

Transition-metal-catalyzed cross-coupling chemistry can be regarded as one of the most powerful protocols to construct carbon–carbon bonds. While the field is still dominated by palladium catalysis, there is an increasing interest to develop protocols that utilize cheaper and more sustainable metal sources. Herein, we report a selective, practical, and fast iron-based cross-coupling reaction that enables the formation of Csp?Csp3 and Csp2?Csp3 bonds. In a telescoped flow process, the reaction can be combined with the Grignard reagent synthesis. Moreover, flow allows the use of a supporting ligand to be avoided without eroding the reaction selectivity.

Iron-Catalyzed e?Selective dehydrogenative borylation of vinylarenes with pinacolborane

We report the dehydrogenative borylation of vinylarenes with pinacolborane (HBpin) catalyzed by an iron(0) complex “(PMe3)4Fe”. A variety of monosubstituted and disubstituted vinylarenes underwent this iron-catalyzed transformation, affording E-vinyl boronate esters (VBEs) selectively in hi h ields. In addition we coupled this iron-catal zed dehydrogenative borylation with further transformations of the resulting vinyl boronate esters and developed various one-pot procedures for the functionalization of the vinylic C?H bonds in vinylarenes. Mechanistic studies reveal that this Fe-catalyzed reaction proceeds through syn-insertion of vinylarenes into a Fe-boryl species followed by β-hydrogen elimination from a syn coplanar conformation of the borylalkyl iron intermediate.

Efficient halogenation of unsaturated organoaluminum compounds with sulfonyl halides

Alkenylalumanes prepared by carbo-or cycloalumination of substituted acetylenes reacted with an equivalent amount of sulfonyl halide (MsCl, TsCl, PhSO2Cl, MsBr) in methylene chloride or hexane at room temperature to produce alkenyl halides in high yields. Electron-donor solvents such as diethyl ether or tetrahydrofuran inhibited the halogenation process. β-Substituted vinylalumanes generated by hydroalumination of substituted acetylenes failed to react with sulfonyl halides.

Direct alkenylation of arylamines at the ortho-position with magnesium alkylidene carbenoids and some theoretical studies of the reactions

1-Chlorovinyl p-tolyl sulfoxides were synthesized from ketones and chloromethyl p-tolyl sulfoxide in high yields. Treatment of the sulfoxides with isopropylmagnesium chloride at -78°C in toluene gave magnesium alkylidene carbenoids (α-chloro alkenylmagnesium chlorides), which were treated with N-lithio arylamines to afford ortho-alkenylated arylamines in moderate yields. The reaction, in some cases, proceeded in a highly stereospecific manner at the carbon bearing the chlorine and the sulfinyl group. The structures of the α-chloro alkenylmagnesium chlorides and the reactivity of the N-lithio meta-substituted anilines were studied at the B3LYP and MP2 levels of theory with the 6-31(+)G* basis set. This reaction offers a quite novel and direct alkenylation of arylamines at the ortho-position of the aromatic ring.

Magnesium alkylidene carbenoids: Generation from 1-halovinyl sulfoxides with Grignard reagents and studies on their property, mechanism, and some synthetic uses

Magnesium alkylidene carbenoids were generated from 1-halovinyl sulfoxides, derived from ketones and aryl halomethyl sulfoxide, through the ligand exchange reaction of sulfoxides with Grignard reagents. The generated magnesium alkylidene carbenoids were found to be stable at -78 °C for over 30 min. The carbenoids reacted with aldehydes to give the adducts in moderate yields; however, they were found to be relatively unreactive to usual electrophiles. The generated magnesium alkylidene carbenoid exists in equilibrium between an α-halo alkenyl Grignard reagent and an alkylidene carbene-magnesium halide complex. Halogen exchange and geometrical isomerization of the alkylidene carbenoids were observed. 1-Chlorovinyl sulfoxides reacted with excess aryl Grignard reagents to give alkenyl Grignard reagents having an aryl group. These Grignard reagents reacted with several electrophiles to give tetra-substituted olefins in moderate to good yields.

Synthesis of Mono and gem-Dihalogeno-olefins from Carbonyl Compounds and in situ Generated Lithium Carbenoids

The treatment of carbonyl compounds (5) with dihalogenomethane and lithium dicyclohexylamide at -78 deg C leads after acid hydrolysis to the crude alcohols (6), which by silylation with trimethylchlorosilane-hexamethyldisilazane-pyridine affords the crude

Evidence for Protonation of Typically Electrophilic Carbenes by Methanol

Deuterium was incorporated in the alkenes formed by 1,2-H migration in phenyl- and chloro-carbenes generated in MeOD.

TEMPERATURE AND MATRIX EFFECTS ON COMPETITIVE INTERMOLECULAR AND INTRAMOLECULAR REACTION OF BENZYLCHLOROCARBENES IN ETHANOL

Benzylchlorocarbenes generated photolytically from diazirines in EtOH afford chlorostyrenes and acetals, whose distributions are sensitive to the reaction temperature.