1530-19-4

Upstream product

• 5384-59-8 1,1-diphenylhexan-1-ol 
• 22932-00-9 Acetic acid 1-(hydroxy-diphenyl-methyl)-pentyl ester 
• 592-41-6 1-hexene 
• 1450-31-3 Thiobenzophenon 
• 119-61-9 benzophenone 
• 83021-61-8 (E)-diisobutyl(pent-1-enyl)aluminum 
• 146511-36-6 1-<<(6,6-diphenyl-5-hexenyl)carbonyl>oxy>-2(1H)-pyridinethione 
• 530-48-3 1,1-Diphenylethylene 
• 109-72-8 n-butyllithium 
• 5232-99-5 etocrylene 
• 167562-69-8 6,6-diphenyl-5-hexenyl bromide 
• 645-96-5 Benzeneselenol 
• 146511-35-5 6,6-diphenyl-5-hexenyl radical 
• 75-66-1 2-methylpropan-2-thiol 

Downstream Products

• 1530-04-7 1,1-diphenyl hexane 
• 22932-08-7 1,1-Diphenyl-1,2-hexandiol 

Relevant academic research and scientific papers

OLEFINATION OF KETONES USING 1,1-DIMETALLOALKANES DERIVED FROM i-Bu2AlCH=CHR - Cl2TiCp2 SYSTEM

The alkylidenation of ketone carbonyls using 1,1-dimetalloalkanes prepared by the reaction of 1-alkenyldiisobutylalanes with titanocene dichloride afforded the corresponding olefins in good yields.

Radical clock reactions under Pseudo-first-order conditions using catalytic quantities of dipnenyl diselenide. A 77Se- and 119Sn-NMR study of the reaction of tributylstannane and diphenyl diselenide

A method for the trapping of alkyl radicals by constant, catalytic quantities of PhSeH as a clock reaction in radical kinetics is presented. PhSeH is introduced in the form of PhSeSePh and regenerated by slow addition of a stoichiometric quantity of Bu3SnH. Using this method the rate constant for cyclization of the 6,6-diphenyl-5-hexenyl radical was found to be 6.8 × 107 s-1 at 20 °C, in fair agreement with the literature value of 4 × 107 s-1. An extension of the method was used to determine the rate of quenching of the 2,3,4,6-tetra-O-acetoxy-1-glucosyl radical by PhSeH as 3.6 × 106 s-1 at 78°C. The reaction of Bu3nH and PhSeSePh was studied by a combination of 77Se- and 119Sn-NMR spectroscopy.

Direct Deamination of Primary Amines via Isodiazene Intermediates

We report here a reaction that selectively deaminates primary amines and anilines under mild conditions and with remarkable functional group tolerance including a range of pharmaceutical compounds, amino acids, amino sugars, and natural products. An anomeric amide reagent is uniquely capable of facilitating the reaction through the intermediacy of an unprecedented monosubstituted isodiazene intermediate. In addition to dramatically simplifying deamination compared to existing protocols, our approach enables strategic applications of iminium and amine-directed chemistries as traceless methods. Mechanistic and computational studies support the intermedicacy of a primary isodiazene which exhibits an unexpected divergence from previously studied secondary isodiazenes, leading to cage-escaping, free radical species that engage in a chain, hydrogen-atom transfer process involving aliphatic and diazenyl radical intermediates.

Alkene homologation: via visible light promoted hydrophosphination using triphenylphosphonium triflate

A hydrophosphination reaction of alkenes with triphenylphosphonium triflate under photocatalytic conditions is described. The reaction is promoted by naphthalene-fused N-acylbenzimidazole and is believed to proceed through intermediate formation of a phosphinyl radical cation. The resulting phosphonium salts are directly involved in the Wittig reaction leading to homologated alkenes.

Conversion of Carbonyl Compounds to Olefins via Enolate Intermediate

A general and efficient protocol to synthesize substituted olefins from carbonyl compounds via nickel catalyzed C—O activation of enolates was developed. Besides ketones, aldehydes were also suitable substrates for the presented catalytic system to produce di- or tri- substituted olefins. It is worth noting that this approach exhibited good tolerance to highly reactive tertiary alcohols, which could not survive in other reported routes for converting carbonyl compounds to olefins. This method also showed good regio- and stereo-selectivity for olefin products. Preliminary mechanistic studies indicated that the reaction was accomplished through nickel catalyzed C—O activation of enolates, thus offering helpful contribution to current enol chemistry.

Hydropersulfides: H-Atom Transfer Agents Par Excellence

Hydropersulfides (RSSH) are formed endogenously via the reaction of the gaseous biotransmitter hydrogen sulfide (H2S) and disulfides (RSSR) and/or sulfenic acids (RSOH). RSSH have been investigated for their ability to store H2S in vivo and as a line of defense against oxidative stress, from which it is clear that RSSH are much more reactive to two-electron oxidants than thiols. Herein we describe the results of our investigations into the H-atom transfer chemistry of RSSH, contrasting it with the well-known H-atom transfer chemistry of thiols. In fact, RSSH are excellent H-atom donors to alkyl (k ～ 5 × 108 M-1 s-1), alkoxyl (k ～ 1 × 109 M-1 s-1), peroxyl (k ～ 2 × 106 M-1 s-1), and thiyl (k > 1 × 1010 M-1 s-1) radicals, besting thiols by as little as 1 order and as much as 4 orders of magnitude. The inherently high reactivity of RSSH to H-atom transfer is based largely on thermodynamic factors; the weak RSS-H bond dissociation enthalpy (～70 kcal/mol) and the associated high stability of the perthiyl radical make the foregoing reactions exothermic by 15-34 kcal/mol. Of particular relevance in the context of oxidative stress is the reactivity of RSSH to peroxyl radicals, where favorable thermodynamics are bolstered by a secondary orbital interaction in the transition state of the formal H-atom transfer that drives the inherent reactivity of RSSH to match that of α-tocopherol (α-TOH), nature's premier radical-trapping antioxidant. Significantly, the reactivity of RSSH eclipses that of α-TOH in H-bond-accepting media because of their low H-bond acidity (α2H ～ 0.1). This affords RSSH a unique versatility compared to other highly reactive radical-trapping antioxidants (e.g., phenols, diarylamines, hydroxylamines, sulfenic acids), which tend to have high H-bond acidities. Moreover, the perthiyl radicals that result are highly persistent under autoxidation conditions and undergo very rapid dimerization (k = 5 × 109 M-1 s-1) in lieu of reacting with O2 or autoxidizable substrates.

Ruthenium(II)-catalyzed olefination: Via carbonyl reductive cross-coupling

Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KOtBu and bidentate phosphine dmpe is vital to this transformation.

Unexpected and powerful effect of chlorobenzene in direct palladium-catalyzed cascade Sonogashira-hydroarylation reaction

A ubiquitous accelerating effect of chlorobenzene (PhCl) was observed unexpectedly in the Pd-catalyzed cascade Sonogashira-hydroarylation reaction. This new type of carbon-carbon bond forming cross-coupling reaction was efficiently catalysed by Pd2(dba)3 in the presence of a catalytic amount of PhCl, which provides a facile and direct approach to the synthesis of trisubstituted olefins.

Palladium-catalyzed hydrophenylation of alkynes with sodium tetraphenylborate under mild conditions

(Chemical Equation Presented) In an aqueous solution of acetic acid, PdCl2(PPh3)2 showed high catalytic activity for the hydrophenylation of both terminal and internal alkynes with sodium tetraphenylborate (NaBPh4) under mild conditions, affording phenyl alkenes in moderate to excellent yields.

3,5-Bis(trifluoromethyl)phenyl sulfones in the Julia-Kocienski olefination - Application to the synthesis of tri- and tetrasubstituted olefins

3,5-Bis(trifluoromethyl)phenyl (BTFP) sulfones 8a-d are successfully employed in the modified Julia olefination reaction with carbonyl compounds employing phosphazene base P4-tBu at room temp. in THF, affording tri- and tetrasubstituted olefins in good yi