40595-34-4

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 63883-64-7 C₂₄H₃₄N₂O₂S 
• 71445-63-1 propiophenone benzenesulfonylhydrazone 
• 63922-84-9 2-(trimethylsilyl)ethyltriphenylphosphonium iodide 
• 100-52-7 benzaldehyde 
• 300-57-2 allylbenzene 
• 21087-29-6 trans-3-phenylprop-2-enyl chloride 
• 18000-27-6 trimethylsilyllithium 
• 91899-54-6 (Trimethylsilyl)copper 
• 4392-24-9 Cinnamyl bromide 
• 21040-45-9 Cinnamyl acetate 
• 1450-14-2 1,1,1,2,2,2-hexamethyldisilane 
• 103-64-0 bromostyrene 
• 13170-43-9 (trimethylsilyl)methylmagnesium chloride 

Downstream Products

• 96746-40-6 4-phenyl-5-hexen-1-ol 
• 115546-07-1 5-Phenyl-hept-6-ene-2,4-dione 
• 1476-07-9 (E)-(3-ethoxy-1-propen-1-yl)benzene 
• 14093-65-3 α-phenylallyl ethyl ether 
• 74120-63-1 (E)-1,4-diphenyl-1,5-hexadiene 
• 76524-55-5 (E)-(5-methylhexa-1,5-dienyl)benzene 
• 73222-66-9 (5-methylhexa-1,5-dien-3-yl)benzene 
• 68060-18-4 (4-methylhexa-1,5-dien-3-yl)benzene 
• 76524-56-6 4-methyl-1-phenyl-1,5-hexadiene 
• 82094-55-1 1-Adamantan-1-yl-2-phenyl-but-3-en-1-ol 
• 105140-54-3 (E)-3,3,6,6-Tetramethyl-7-phenyl-nona-4,8-dienal 
• 105140-45-2 ((E)-2,2,5,5-Tetramethyl-1-vinyl-hepta-3,6-dienyl)-benzene 
• 21087-29-6 trans-3-phenylprop-2-enyl chloride 
• 57294-86-7 (E)-cinnamyl azide 

Relevant academic research and scientific papers

Electrophilic difluoro(phenylthio)methylation: Generation, stability, and reactivity of α-fluorocarbocations

Electrophilic difluoro(phenylthio)methylation of allylsilanes has been achieved using bromodifluoro(phenylthio)methane (PhSCF2Br) and silver hexafluoroantimonate (AgSbF6). The structural assignment and observation of α-fluorocarbocation were substantiated by NMR and theoretical calculations. Detailed mechanistic and electronic studies have provided a fundamental understanding of the reactivity and stability of the difluoro(phenylthio)methylium cation (PhSCF2+).

NOVEL REARRANGEMENT OF CHLOROMETHYLVINYLSILANES INTO ALLYLSILANES. STEREOSELECTIVE SYNTHESIS OF METALLATED ALLYLSILANES FROM 1-ALKYNES

Regio and stereoselective hydralumination of 1-(chloromethyldimethylsilyl)-1-alkyne with diisobutylaluminium hydride (DIBAH) affords (Z)-1-(chloromethyldimethylsilyl)-1-(diisobutylalumino)-1-alkene.Treatment of the aluminium-substituted vinylsilane with 3 equivalents of methyllithium affords (E)-1-(trimethylsilyl)-2-lithio-2-alkene as a sole product.Reaction of aluminium-substituted vinylsilane with trimethylaluminium in refluxing heptane produces a mixture of (E)-1-trimethyl-silyl-2-alumino-2-alkene and 2-trimethylsilyl-1-alkene.Reaction of 1-(chloromethyldimethylsilyl)-1-alkyne with triisobutylaluminium gives 2-(isobutyldimethylsilyl)-1-alkene exclusively.Reactions of the lithiated allylsilane with several electrophiles give the corresponding carbometallated products, allylsilanes bearing alkyl, allyl, vinyl, or alkoxycarbonyl groups.Protodesilylation of 3-(trimethylsilylmethyl)-1,3-decadiene gives 3-methylene-1-decene selectively.Reaction of trialkylaluminium with trimethylsilylethyne gives bistrimethylsilylated diene by successive addition of silylethyne to the aluminium reagent; in contrast, chloromethyldimethylsilylethyne gives the mono-adduct regio and stereoselectively.

Diastereoselective Addition of Prochiral Nucleophilic Alkenes to α-Chiral N-Sulfonyl Imines

The Lewis-acid-promoted addition of prochiral E- and Z-allyl nucleophiles to chiral α-alkoxy N-tosyl imines is described. Alkene geometry is selectively transferred to the newly formed carbon-carbon bond, resulting in stereochemical control of C1, C2, and C3 of the resulting 2-alkoxy-3-N-tosyl-4-alkyl-5-hexene products. A computational analysis to elucidate the high selectivity is also presented. This methodology was employed in the synthesis of two naturally occurring isomers of clausenamide.

Oxoammonium-Mediated Allylsilane–Ether Coupling Reaction

A new C(sp3)?H functionalization reaction consisting of the oxidative α-allylation of allyl- and benzyl- methyl ethers has been developed. The C?C coupling could be carried out under mild conditions thanks to the use of cheap and green oxoammonium salts. The scope of the reaction was studied over 27 examples, considering the nature of the substituents on the two coupling partners.

Nickel-Mediated Enantiospecific Silylation via Benzylic C-OMe Bond Cleavage

Benzylic stereocenters are found in bioactive and drug molecules, as enantiopure benzylic alcohols have been used to build such a stereogenic center, but are limited to the construction of a C-C bond. Silylation of alkyl alcohols has the potential to build bioactive molecules and building blocks; however, the development of such a process is challenging and unknown. Herein, we describe an unprecedented AgF-assisted nickel catalysis in the enantiospecific silylation of benzylic ethers.

Stereospecific Iron-Catalyzed Carbon(sp2)-Carbon(sp3) Cross-Coupling with Alkyllithium and Alkenyl Iodides

An efficient synthetic protocol involving iron-catalyzed cross-coupling reactions between organolithium compounds and alkenyl iodides as key coupling partners was achieved. More than 30 examples were obtained with moderate to good yields and high stereospecificity. Gram-scale and synthetic applications of this procedure are recorded herein to demonstrate its feasibility and potential utilization.

N-Heterocyclic Carbene Complexes Of Metal Imido Alkylidenes And Metal OXO Alkylidenes, And The Use Of Same

The invention relates to an N-heterocyclic carbene complex of general formulas I to IV (I) (II) (III) (IV), according to which A1 stands for NR2 or PR2, A2 stands for CR2 R2′, NR2, PR2, 0 or S, A3 stands for N or P, and C stands for a carbene carbon atom, ring B is an unsubstituted or a mono or poly-substituted 5 to 7-membered ring, substituents R2 and R2′ stand, inter alia, for a linear or branched C1-Cw-alkyl group and, if N and N each stand for NR2 or PR2, are the same or different, M in formulas I, II, III or IV stands for Cr, Mo or W, X 1 or X2 in formulas I to IV are the same or different and represent, inter alia, C1-C1s carboxylates and C1-C1s-alkoxides, Y is inter alia oxygen or sulphur, Z is inter alia a linear or branched C1-Cw-alkylenoxy group, and R 1 and R1′ in formulas I to IV are, inter alia, an aliphatic or aromatic group. These compounds are particularly suitable for use as catalysts for olefin metathesis reactions and have the advantage, compared to known Schrock carbene complexes, of displaying clearly increased tolerance to functional groups such as, in particular, aldehydes, secondary amines, nitriles, carboxylic acids and alcohols.

Visible Light-Induced Room-Temperature Heck Reaction of Functionalized Alkyl Halides with Vinyl Arenes/Heteroarenes

The first visible light-induced Pd-catalyzed Heck reaction of α-heteroatom substituted alkyl iodides and -bromides with vinyl arenes/heteroarenes has been developed. This transformation efficiently proceeds at room temperature and enables synthesis of valuable functionalized allylic systems, such as allylic silanes, boronates, germanes, stannanes, pivalates, phosphonates, phthalimides, and tosylates from the corresponding α-substituted methyl iodides. Notably, synthesis of the latter substrates failed under existing thermally induced Pd-catalyzed conditions, which highlights the importance of visible light for this transformation.

METHOD FOR PRODUCING ALLYLSILANE COMPOUND

PROBLEM TO BE SOLVED: To provide a method for producing an allylsilane compound which can efficiently produce an allylsilane compound. SOLUTION: An allylsilane compound can be efficiently produced by the reaction between a halogenated allyl compound and a disilane compound in the presence of a palladium element-containing nanoparticle having solvent coordinated on the surface. SELECTED DRAWING: Figure 2 COPYRIGHT: (C)2017,JPOandINPIT

A Bench-Stable, Single-Component Precatalyst for Silyl-Heck Reactions

Studies of the silyl-Heck reaction aimed at identifying active palladium complexes have revealed a new species that is formed in situ. This complex has been identified as the palladium iodide dimer, [(JessePhos)PdI2]2, which has been