782-05-8

Upstream product

• 22293-10-3 (1-diazoethyl)benzene 
• 22875-84-9 2,3-diphenyl-1-butene 
• 42808-98-0 phenethyllithium 
• 98-86-2 acetophenone 
• 19912-53-9 meso-Bis-α-methylbenzylsulfon 
• 501-65-5 diphenyl acetylene 
• 7664-93-9 sulfuric acid 
• 782-06-9 (E)-2,3-diphenylbutene 
• 917-54-4 methyllithium 
• 75-24-1 trimethylaluminum 
• 60-29-7 diethyl ether 
• 101292-09-5 2-chloro-2,3-diphenyl-butane 
• 7664-41-7 ammonia 
• 105514-72-5 2,3-dibromo-2,3-diphenyl-butane 

Downstream Products

• 61894-39-1 1,1-Dichlor-r-2,c-3-dimethyl-2,t-3-diphenylcyclopropan 
• 78775-58-3 (Z)-3-Chlor-2,4-diphenyl-1,3-pentadien 
• 108774-24-9 (2S*,3R*)-2,3-diphenylbutan-1-ol 
• 782-06-9 (E)-2,3-diphenylbutene 
• 4613-11-0 2,3-diphenylbutane 
• 98-86-2 acetophenone 
• 81052-75-7 (2S,3R,4S,5R)-2,5-Dimethyl-2,5-diphenyl-tetrahydro-furan-3,4-dicarbonitrile 
• 81052-74-6 (2S,3S,4S,5R)-2,5-Dimethyl-2,5-diphenyl-tetrahydro-furan-3,4-dicarbonitrile 
• 240138-15-2 syn-MeCH(Ph)CH(Ph)CH₂BH₂ 
• 99553-73-8 trans-3,5-dimethyl-3,5-diphenyl-1,2,4-trioxolane 
• 99553-73-8 cis-3,5-dimethyl-3,5-diphenyl-1,2,4-trioxolane 
• 1636-34-6 2,3-diphenyl-2,3-butanediol 
• 40188-25-8 2,3-Diphenyl-but-3-en-2-yl-hydroperoxide 
• 86939-05-1 1-Phenyl-1-(3-phenyl-[1,2]dioxetan-3-yl)-eth-1-yl-hydroperoxide 

Relevant academic research and scientific papers

Olefin functionalization/isomerization enables stereoselective alkene synthesis

Despite tremendous efforts aimed at devising methods for stereoselective alkene synthesis, critical challenges are yet to be addressed. Direct access to a diverse range of 1-aryl(boryl)-1-methyl-functionalized tri- and tetrasubstituted trans alkenes, entities that are prevalent in many important molecules, through a catalytic manifold from readily available α-olefin substrates remains elusive. Here, we demonstrate that catalytic amounts of a non-precious N-heterocyclic carbene–Ni(I) complex in conjunction with a sterically bulky base promote site- and trans-selective union of monosubstituted olefins with a wide array of electrophilic reagents to deliver tri- and tetrasubstituted alkenes in up to 92% yield and >98% regio- and stereoselectivity. The protocol is amenable to the preparation of carbon- and heteroatom-substituted C=C bonds, providing distinct advantages over existing transformations. Utility is highlighted through concise stereoselective synthesis of biologically active compounds. [Figure not available: see fulltext.].

Asymmetric Hydrogenation of Unfunctionalized Tetrasubstituted Acyclic Olefins

Asymmetric hydrogenation has evolved as one of the most powerful tools to construct stereocenters. However, the asymmetric hydrogenation of unfunctionalized tetrasubstituted acyclic olefins remains the pinnacle of asymmetric synthesis and an unsolved challenge. We report herein the discovery of an iridium catalyst for the first, generally applicable, highly enantio- and diastereoselective hydrogenation of such olefins and the mechanistic insights of the reaction. The power of this chemistry is demonstrated by the successful hydrogenation of a wide variety of electronically and sterically diverse olefins in excellent yield and high enantio- and diastereoselectivity.

Cathodic reductive couplings and hydrogenations of alkenes and alkynes catalyzed by the B12 model complex

The reductive coupling and hydrogenation of alkenes were catalyzed by the B12 model complex, heptamethyl cobyrinate perchlorate (1), in the presence of acid during electrolysis at??0.7?V vs. Ag/AgCl in acetonitrile. Conjugated alkenes showed a good reactivity during electrolysis to form reduced products. The product distributions were dependent on the substituents at the C[dbnd]C bond of the alkenes. ESR spin-trapping experiments using 5,5-dimethylpyrroline N-oxide (DMPO) revealed that the cobalt-hydrogen complex (Co–H complex) should be formed during the electrolysis and it functioned as an intermediate for the alkene reduction. The electrolysis was also applied to an alkyne, such as phenylacetylene, to form 2,3-diphenylbutane (racemic and meso) and ethylbenzene via styrene as reductive coupling and hydrogenated products, respectively.

Transition-metal-free synthesis of 1,1-diboronate esters with a fully substituted benzylic center via diborylation of lithiated carbamates

A transition-metal-free lithiation-borylation method has been developed to access a variety of 1,1-diboronate esters with a fully substituted benzylic center from readily available secondary benzylic N,N-diisopropyl carbamates. The method is applicable to scale-up synthesis of 1,1-diboron compounds. Furthermore, the current method is also applicable to synthesizing optically active 1,1-silylboronate esters.

A heterobimetallic complex featuring a Ti-Co multiple bond and its application to the reductive coupling of ketones to alkenes

To explore metal-metal multiple bonds between first row transition metals, Ti/Co complexes supported by two phosphinoamide ligands have been synthesized and characterized. The Ti metalloligand Cl2Ti(XylNPiPr2)2 (1) was treated with CoI2 under reducing conditions, permitting isolation of the Ti/Co complex [(μ-Cl)Ti(XylNPiPr2)2CoI]2 (2). One electron reduction of complex 2 affords ClTi(XylNPiPr2)2CoPMe3 (3), which features a metal-metal triple bond and an unprecedentedly short Ti-Co distance of 2.0236(9) ?. This complex is shown to promote the McMurry coupling reaction of aryl ketones into alkenes, with concomitant formation of the tetranuclear complex [Ti(μ3-O)(NXylPiPr2)2CoI]2 (4). A cooperative mechanism involving bimetallic C=O bond activation and a cobalt carbene intermediate is proposed.

Reductive coupling of carbonyl compounds promoted by cobalt or titanium nanoparticles

The reaction of a series of aldehydes and ketones with readily prepared cobalt or titanium nanoparticles, under mild reaction conditions, led to the obtention of different reductive dimerization products depending on the nature of the transition metal used. Cobalt nanoparticles (CoNPs) allowed the selective transformation of the starting carbonyl compounds into vicinal diols, whereas the reaction promoted by titanium nanoparticles (TiNPs) led to the formation of the corresponding alkenes. In this last case, the use of trimethylsilyl chloride (TMSCl) as additive, at 0 °C, also allowed the obtention of vicinal diols after acidic aqueous work-up. ARKAT-USA, Inc.

Stereoselective synthesis of tetrasubstituted alkenylboronates via 1,1-organodiboronates

The stereoselective synthesis of tetrasubstituted alkenylboronates was established via the lithiation/nucleophilic addition reaction of 1,1-organodiboronates to carbonyl compounds. The present approach enables the facile and practical synthesis of tetrasu

McMurry coupling of aryl aldehydes and imino pinacol coupling mediated by Ti(O-i-Pr)4/Me3SiCl/Mg reagent

Ti(O-i-Pr)4/Me3SiCl/Mg reagent mediated McMurry coupling of aryl aldehydes to biaryl olefins at near room temperature. This low valent titanium (LVT) reagent also mediated the coupling of aldimines to 1,2-diamines (imino pinacol coupling).

Salt/ligand-activated low-valent titanium formulations: the 'salt effect' on diastereoselective carbon-carbon bond forming SET reactions

A comprehensive study on the influence of exogenously added electropositive metal salts as promoters/secondary activators on preformed LVT species has resulted in the construction of highly efficient low-valent titanium (LVT) reagents. These salt-activated LVT reagents while exhibiting enhanced chemoselectivity and diastereoselectivity accelerated the reductive olefination rates of aromatic and aliphatic carbonyls under ambient temperature conditions and in much reduced reaction times. The versatility of the salted reagent was further explored in other single electron transfer reactions, namely, imino-pinacol couplings and one-pot synthesis of phenanthrenes from o-alkoxy aromatic carbonyls. We envisage that, in contrast to multiphase heterogeneous colloidal slurries, salt-activated LVT reagents afforded uniformly viscous homogeneous slurries generating a highly reactive monomeric intermetallic LVT complex. Continued judicious exploration of the emerging paradigms by studying the influence of external ligands/auxiliaries/redox agents on LVT reagents, and organometallics in general, will be critical to widen the scope and utility of the classical McMurry reaction and other SET reactions.

Ionic-liquid-influenced expeditious and stereoselective synthesis of olefins

1-Butyl-3-methylimidazolium chloroaluminate, [bmim]Cl·.AlCl3 (molar fraction, N=0.67), ionic liquid has been used in combination with metallic Zn for the reductive coupling of carbonyl compounds to synthesize symmetrical olefins, with the Z-isomer formed predominantly. The ionic liquid played a dual role of Lewis acid catalyst and solvent. Copyright Taylor & Francis Group, LLC.