782-06-9

Upstream product

• 5769-02-8 2-methyl-2-phenyl[1,3]dithiolane 
• 782-05-8 (Z)-2,3-diphenyl-2-butene 
• 2575-20-4 3,3-diphenylbutan-2-one 
• 101292-09-5 2-chloro-2,3-diphenyl-butane 
• 5616-55-7 2-phenyl-1,3-dithiane 
• 172-16-7 indanone dithioacetal 
• 42196-84-9 3',4'-dihydro-2'H-spiro[1,3-dithiolane-2,1'-naphthalene] 
• 22293-10-3 (1-diazoethyl)benzene 
• 769-59-5 3-phenyl-butan-2-one 
• 22875-84-9 2,3-diphenyl-1-butene 
• 41563-48-8 (2,2-diphenylethene-1,1-diyl)bis(phenylsulfane) 
• 19557-70-1 3.3.1.1^3,7.tricyclo 2-decane 2'-spiro(1',3'-dithiolanne) 
• 124688-02-4 6-methoxy-2,3-dihydrospiro[Indene-1,2’-[1,3]dithiolane] 
• 123994-14-9 (E)-2,3-bis(2-bromophenyl)-2-butene 

Downstream Products

• 105514-72-5 2,3-dibromo-2,3-diphenyl-butane 
• 7781-70-6 1,4-dibromo-2,3-diphenyl-2-butene 
• 781-33-9 2-methyl-1,1-diphenylpropene 
• 78775-45-8 (E)-3-Fluor-2,4-diphenyl-1,3-pentadien 
• 54398-02-6 1,1-Dichlor-r-2,t-3-dimethyl-2,c-3-diphenylcyclopropan 
• 40188-25-8 2,3-Diphenyl-but-3-en-2-yl-hydroperoxide 
• 495-45-4 dypnone 
• 40188-27-0 2,3-Diphenylbut-3-en-2-ol 
• 89867-88-9 3,3-Diphenyl-4-hydroxy-2-butanone 
• 86939-06-2 (R^*,R^*)-α,2-Diphenyl-α-methyloxiranemethanol 
• 86939-06-2 (R^*,S^*)-α,2-Diphenyl-α-methyloxiranemethanol 
• 99553-73-8 cis-3,5-dimethyl-3,5-diphenyl-1,2,4-trioxolane 
• 99553-73-8 trans-3,5-dimethyl-3,5-diphenyl-1,2,4-trioxolane 
• 4539-31-5 (2S,3S)-2,3-dimethyl-2,3-diphenyloxirane 

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.

Copper-catalyzed aerobic oxidative transformation of ketone- Derived N-tosyl hydrazones: An entry to alkynes

A novel strategy involving Cu-catalyzed oxidative transformation of ketone-derived hydrazone moiety to various synthetic valuable internal alkynes and diynes has been developed. This method features inexpensive metal catalyst, green oxidant, good functional group tolerance, high regioselectivity and readily available starting materials. Oxidative deprotonation reactions were carried out to form internal alkynes and symmetrical diynes. Cross-coupling reactions of hydrazones with halides and terminal alkynes were performed to afford functionalized alkynes and unsymmetrical conjugated diynes. A mechanism proceeding through a Cu-carbene intermediate is proposed for the CC triple bond formation.

What molecules are likely or unlikely to undergo pedal motions in crystals?

The crystal structures of several (E)-stilbenes and 1,2-diarylethane that have methyl or chloro substituents were examined by variable-temperature X-ray diffraction analysis. All the compounds showed disorders in their crystal structures at least at room

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.

Weakening C-O bonds: Ti(III), a new reagent for alcohol deoxygenation and carbonyl coupling olefination

Investigations detailed herein, including density functional theory (DFT) calculations, demonstrate that the formation of either alkoxy- or hydroxy-Ti(III) complexes considerably decreases the energy of activation for C-O bond homolysis. As a consequence of this observation, we described two new synthetic applications of Nugent's reagent in organic chemistry. The first of these applications is an one-step methodology for deoxygenation-reduction of alcohols, including benzylic and allylic alcohols and 1,2-dihydroxy compounds. Additionally, we have also proved that Ti(III) is capable of mediating carbonyl coupling-olefination. In this sense, and despite the fact that for over 35 years it has been widely accepted that either Ti(II) or Ti(0) was the active species in the reductive process of the McMurry reaction, the mechanistic evidence presented proves the involvement of Ti(III) pinacolates in the deoxygenation step of the herein described Nugent's reagent-mediated McMurry olefination. This observation sheds some light on probably one of the mechanistically more complex transformations in organic chemistry. Finally, we have also proved that both of these processes can be performed catalytically in Cp 2TiCl2 by using trimethylsilyl chloride (TMSCl) as the final oxygen trap.

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).