559062-83-8

Upstream product

• 623-73-4 diazoacetic acid ethyl ester 
• 122-78-1 phenylacetaldehyde 
• 1530-45-6 (carbethoxymethyl)triphenylphosphonium bromide 
• 100-39-0 benzyl bromide 
• 82101-76-6 (Z)-ethyl 3-(tributylstannyl)propenoate 
• 100-44-7 benzyl chloride 
• 31930-34-4 ethyl (Z)-3-bromopropenoate 
• 16490-99-6 ethyl (Z)-3-chloro-2-propenoate 
• 623-47-2 propynoic acid ethyl ester 
• 82830-86-2 ethyl 2-diazo-4-phenylbutanoate 
• 867-13-0 diethoxyphosphoryl-acetic acid ethyl ester 
• 1099-45-2 ethyl (triphenylphosphoranylidene)acetate 

Downstream Products

• 78571-81-0 (R,R)-3-(phenylmethyl)oxiranemethanol 
• 78571-81-0 (2S-trans)-3-(Phenylmethyl)oxiranemethanol 
• 420843-10-3 cis-1-bromo-4-phenyl-2-butene 
• 22910-59-4 (Z)-4-phenylbut-2-en-1-ol 
• 42238-15-3 (2E)-4-phenylbut-2-en-1-ol 

Relevant academic research and scientific papers

Tris(pentafluorophenyl)borane-Catalyzed Oxygen Insertion Reaction of α-Diazoesters (α-Diazoamides) with Dimethyl Sulfoxide

A tris(pentafluorophenyl)borane-catalyzed oxidation reaction of α-diazoesters (α-diazo amides) with dimethyl sulfoxide has been developed. The reaction proceeds under metal free conditions to afford a series α-ketoesters and α-ketoamides. The synthetic utility of this protocol is demonstrated through synthetic transformations and scaled-up synthesis. (Figure presented.).

Engaging Alkenyl Halides with Alkylsilicates via Photoredox Dual Catalysis

Single-electron transmetalation via photoredox/nickel dual catalysis provides the opportunity for the construction of Csp3-Csp2 bonds through the transfer of alkyl radicals under very mild reaction conditions. A general procedure for the cross-coupling of primary and secondary (bis-catecholato)alkylsilicates with alkenyl halides is presented. The developed method allows not only alkenyl bromides and iodides but also previously underexplored alkenyl chlorides to be employed. (Chemical Equation Presented).

AsCat and FurCat: New Pd catalysts for selective roomerature Stille cross-couplings of benzyl chlorides with organostannanes

Two novel succinimide-based palladium complexes, AsCat and FurCat, are highly efficient catalysts for roomerature Stille cross-coupling of organostannanes with benzyl chlorides. The air- and moisture-stable catalysts are prepared in one step, and the coupling reactions proceed with a high selectivity for the benzyl position under mild conditions without the need for additives. This journal is

Dynamic kinetic asymmetric transformations of β-stereogenic α-ketoesters by direct aldolization

Dynamic kinetic asymmetric transformations (DyKAT) of racemic β-bromo-α-keto esters by direct aldolization of nitromethane and acetone provide access to fully substituted α-glycolic acid derivatives bearing a β-stereocenter. The aldol adducts are obtained

Cu(II)-Catalyzed Olefin Migration and Prins Cyclization: Highly Diastereoselective Synthesis of Substituted Tetrahydropyrans

Metal-ligand complexes of Cu(OTf)2 with an appropriate bisphosphine ligand have been shown to effectively catalyze the formation of substituted tetrahydropyrans via a sequential olefin migration and Prins-type cyclization. This methodology provides convenient access to a variety of functionalized tetrahydropyrans in excellent diastereoselectivities and good to excellent yields.

Air-stable, phosphine-free anionic palladacyclopentadienyl catalysts: Remarkable halide and pseudohalide effects in Stille coupling

The Stille cross-coupling of allylic and benzyl bromides is shown to proceed efficiently using phosphine-free dinuclear anionic palladacyclopentadienyl catalysts possessing bridging (N,O)-imidate ligands. The type of bridging anion influences the catalytic activity considerably. Halide anions such as chloride, bromide or iodide also influence the catalytic activity but to a far lesser extent than the pseudohalide imidate anions (from succinimide or phthalimide). A Baldwin-type cooperative effect is seen with 7a using CuI as a co-catalyst, in the presence of two equivalents of CsF in DMF at 40°C. In toluene, these additives slow down substrate turnover. Wiley-VCH Verlag GmbH & Co. KGaA.

Oxidative addition of N-halosuccinimides to palladium(0): The discovery of neutral palladium(II) imidate complexes, which enhance Stille coupling of allylic and benzylic halides

The Stille coupling of organostannanes and organohalides, mediated by air and moisture stable palladium(II) phosphine complexes containing succinimide or phthalimide (imidate) ligands, has been investigated. An efficient synthetic route to several palladium(II) complexes containing succinimide and phthalimide ligands, has been developed. cis-Bromobis(triphenylphosphine)(N-succinimide) palladium(II) [(Ph3P)2Pd(N-Succ)Br] is shown to mediate the Stille coupling of allylic and benzylic halides with alkenyl, aryl and allyl stannanes. In competition experiments between 4-nitrobromobenzene and benzyl bromide with a cis-stannylvinyl ester, (Ph3P)2Pd(N-Succ)Br preferentially cross-couples benzyl bromide, whereas with other commonly employed precatalysts 4-nitrobromobenzene undergoes preferential cross-coupling. Furthermore, preferential reaction of deactivated benzyl bromides over activated benzyl bromides is observed for the first time. The type of halide and presence of a succinimide ligand are essential for effective Stille coupling. The type of phosphine ligand is also shown to alter the catalytic activity of palladium(II) succinimide complexes.

Palladacyclopentadiene complexes with mono- and didentate imidato ligands: Synthesis, hemilabile behaviour and catalytic application in the stille reaction

The binuclear hydroxo complex [NBu4]2[Pd 2(C4(COOMe)4)2-(μ-OH) 2] (1) has been prepared by addition of two equivalents of NBu 4OH to polymeric [Pd{C4(COOMe)4}]n. Complex 1 has been successfully employed as a precursor to three novel binuclear imidate-bridged complexes [NBu4]2[Pd2-(C 4(COOMe)4)2(μ-imidate)2] [imidate = succinimidate (sue) 2, phthalimidate (pht) 3 or maleimidate (mal) 4] in which the imidate group displays a bidentate N,O-coordination mode. The hemilabile behaviour of the imidate ligands has been investigated by reaction with a variety of P, N and S ligands, affording the corresponding mononuclear derivatives [NBu4][Pd{C4(COOMe)4}(imidate)L] [L = PPh3 (2a, 3a or 4a), P(p-C6H4F)3 (2b, 3b or 4b), PBu3 (2c, 3c or 4c), py (2d, 3d or 4d), p-MeC 6H4NH2 (2e, 3e or 4e), tetrahydrothiophene (2f, 3f or 4f)] with terminal N-bonded imidate ligands. The characterization of the new complexes involved spectroscopic methods (IR, FAB, 1H, 13C, 19F and 31P NMR) and X-ray crystallographic analysis for 1, 4b and 4e. The mononuclear derivatives are shown to catalyse the Stille cross-coupling of benzyl bromide 7 with ethyl Z-vinylstannyl carboxylate (8) in high yields. Yields and reaction times are dependent on the presence and type of imidate ligand, which suggests an important role for it in the catalytic cycle. Wiley-VCH Verlag GmbH and Co. KGaA, 69451 Weinheim, Germany, 2004.

Efficient and selective Stille cross-coupling of benzylic and allylic bromides using bromobis(triphenylphosphine)(N-succinimide)palladium(II)

Allylic and benzylic bromides are cross-coupled with organostannanes efficiently using the precatalyst [Pd(NCOC2H4CO)(PPh 3)2Br] 1. Significantly, these reactions do not require the use of hexamethylphosphoramide (HMPA) as the solvent, or additional ligands, such as trifurylphosphine or triphenylarsine. Selectivity for benzyl bromide over bromobenzene is observed for precatalyst 1, against the precatalysts, bromobis(triphenylphosphine)(benzyl)palladium(II) and bis(triphenylphosphine) palladium(II) bromide.

Bromobis(triphenylphosphine)(N-succinimide)palladium(II) as a novel catalyst for Stille cross-coupling reactions

A new palladium catalyst is reported for Stille cross-coupling, namely [Pd(NCOC2H4CO)(PPh3)2Br].