4396-98-9

Upstream product

• 112564-69-9 (+/-)-2-hydroxy-2-phenyl-hexadiene-(3.5) 
• 2720-47-0 2-phenyl-hex-5-en-3-yn-2-ol 
• 109-72-8 n-butyllithium 
• 98-86-2 acetophenone 
• 35322-45-3 3-methyl-3-phenyl-1,2-dioxetane 
• 3674-77-9 2-methyl-2-phenyl-1,3-dioxolane 
• 119-61-9 benzophenone 
• 693-03-8 n-butyl magnesium bromide 
• 100-52-7 benzaldehyde 
• 138857-99-5 C₁₁H₁₆MgO₃S 
• 78350-68-2 chlorotitanium triisopropoxide 
• 542-69-8 1-iodo-butane 
• 109-65-9 1-bromo-butane 
• 591-50-4 iodobenzene 

Downstream Products

• 859185-11-8 methyl-(1-methyl-1-phenyl-pentyl)-ether 
• 20247-89-6 cis/trans-2-phenyl-hex-2-ene 
• 6031-02-3 2-phenylhexane 
• 20826-80-6 2-phenylhex-1-ene 
• 225094-45-1 2-(1-Methyl-1-phenyl-pentyloxy)-tetrahydro-pyran 
• 191479-34-2 (+/-)-2-phenylhex-2-yl hydroperoxide 
• 2955-41-1 (+/-)-2-methyl-2-phenyl-hexanoic acid 
• 36789-51-2 2-methyl-1,2-diphenyl-hexan-1-one 
• 2955-41-1 (+)-2-methyl-2-phenyl-hexanoic acid-⁽¹⁾ 
• 357192-59-7 4-(1-methylpentyl)aniline 
• 1033757-74-2 C₂₁H₂₅N 
• 1033757-81-1 C₂₆H₂₇N 
• 1033757-76-4 C₂₂H₂₅NO₂ 
• 98-85-1 1-Phenylethanol 

Relevant academic research and scientific papers

Iron-catalysed 1,2-aryl migration of tertiary azides

1,2-Aryl migration of α,α-diaryl tertiary azides was achieved by using the catalytic system of FeCl2/N-heterocyclic carbene (NHC) SIPr·HCl. The reaction generated aniline products in good yields after one-pot reduction of the migration-resultant imines.

Continuous Flow Synthesis of Terminal Epoxides from Ketones Using in Situ Generated Bromomethyl Lithium

A scalable procedure for the direct preparation of epoxides from ketones has been developed. The method is based on the carefully controlled generation of (bromomethyl)lithium (LiCH2Br) from inexpensive CH2Br2 and MeLi in a continuous flow reactor. The reaction has shown excellent selectivity for a variety of substrates, including α-chloroketones, which typically fail under classic Corey-Chaykovsky conditions. This advantage has been used to develop a novel route toward the drug fluconazole.

Cis -Oxoruthenium complexes supported by chiral tetradentate amine (N4) ligands for hydrocarbon oxidations

We report the first examples of ruthenium complexes cis-[(N4)RuIIICl2]+ and cis-[(N4)RuII(OH2)2]2+ supported by chiral tetradentate amine ligands (N4), together with a high-valent cis-dioxo complex cis-[(N4)RuVI(O)2]2+ supported by the chiral N4 ligand mcp (mcp = N,N′-dimethyl-N,N′-bis(pyridin-2-ylmethyl)cyclohexane-1,2-diamine). The X-ray crystal structures of cis-[(mcp)RuIIICl2](ClO4) (1a), cis-[(Me2mcp)RuIIICl2]ClO4 (2a) and cis-[(pdp)RuIIICl2](ClO4) (3a) (Me2mcp = N,N′-dimethyl-N,N′-bis((6-methylpyridin-2-yl)methyl)cyclohexane-1,2-diamine, pdp = 1,1′-bis(pyridin-2-ylmethyl)-2,2′-bipyrrolidine)) show that the ligands coordinate to the ruthenium centre in a cis-α configuration. In aqueous solutions, proton-coupled electron-transfer redox couples were observed for cis-[(mcp)RuIII(O2CCF3)2]ClO4 (1b) and cis-[(pdp)RuIII(O3SCF3)2]CF3SO3 (3c′). Electrochemical analyses showed that the chemically/electrochemically generated cis-[(mcp)RuVI(O)2]2+ and cis-[(pdp)RuVI(O)2]2+ complexes are strong oxidants with E° = 1.11-1.13 V vs. SCE (at pH 1) and strong H-atom abstractors with DO-H = 90.1-90.8 kcal mol-1. The reaction of 1b or its (R,R)-mcp counterpart with excess (NH4)2[CeIV(NO3)6] (CAN) in aqueous medium afforded cis-[(mcp)RuVI(O)2](ClO4)2 (1e) or cis-[((R,R)-mcp)RuVI(O)2](ClO4)2 (1e?), respectively, a strong oxidant with E(RuVI/V) = 0.78 V (vs. Ag/AgNO3) in acetonitrile solution. Complex 1e oxidized various hydrocarbons, including cyclohexane, in acetonitrile at room temperature, affording alcohols and/or ketones in up to 66% yield. Stoichiometric oxidations of alkenes by 1e or 1e? in tBuOH/H2O (5:1 v/v) afforded diols and aldehydes in combined yields of up to 98%, with moderate enantioselectivity obtained for the reaction using 1e?. The cis-[(pdp)RuII(OH2)2]2+ (3c)-catalysed oxidation of saturated C-H bonds, including those of ethane and propane, with CAN as terminal oxidant was also demonstrated.

Reactions of organoboranes with carbanions bearing three potential leaving groups: unusual processes, products and mechanisms

Known reagents that transfer three alkyl groups of a trialkylborane intramolecularly to a single carbon atom lack features to influence stereochemistry. We have investigated four reagents of type LiCCl2X, where X might be amenable to variation. All behaved differently. With X=OR (R=cyclohexyl, menthyl), the reagent decomposed, leading to only low yields of triple migration products. With X=S(O)Ph, a single migration occurred, followed by isomerisation to boron enolate-like species that hydrolysed to α-chloroalkyl phenyl sulfoxides or reacted with aldehydes to aldol-like products. With X=SO2Ph, the major product was the corresponding α,α-dichloroalkyl phenyl sulfone, apparently formed through a redox reaction. With X=S(O)(NMe)Ph, products of three intramolecular alkyl migrations were obtained with unhindered trialkylboranes. Attempts have been made to gain understanding of the sulfoxide process by investigating proportions of aldol-like products, using X-ray crystallography and ab initio calculations.

On the scope of the Pt-catalyzed Srebnik diborylation of diazoalkanes. An efficient approach to chiral tertiary boronic esters and alcohols via B-stabilized carbanions

Conditions milder than those previously reported are shown to be generally applicable to the Pt-catalyzed insertion of non-carbonyl-stabilized diazoalkanes into B2pin2. Selective transformation of one (pinacolato)boryl unit in the products is enabled by rapid, low-temperature deboronation in the presence of a Lewis base and genesis of a highly reactive B-stabilized carbanion.

Copper-catalyzed aerobic aliphatic C-H oxygenation with hydroperoxides

We report herein Cu-catalyzed aerobic oxygenation of aliphatic C-H bonds with hydroperoxides, which proceeds by 1,5-H radical shift of putative oxygen-centered radicals (O-radicals) derived from hydroperoxides followed by trapping of the resulting carboncentered radicals with molecular oxygen.

Added-metal-free catalytic nucleophilic addition of Grignard reagents to ketones

On the basis of the investigation of the combinational effect of quaternary ammonium salts and organic bases, an added-metal-free catalytic system for nucleophilic addition reactions of a variety of Grignard reagents to diverse ketones in THF solvent has been developed to produce tertiary alcohols in good to excellent yields. By using tetrabutylammonium chloride (NBu4Cl) as a catalyst and diglyme (DGDE) as an additive, this system strongly enhances the efficiency of addition at the expense of enolization and reduction. NBu 4Cl should help to shift the Schlenk equilibrium of Grignard reagents to the side of dimeric Grignard reagents to favor the additions of Grignard reagents to ketones via a favored six-membered transition state to form the desired tertiary alcohols, and DGDE should increase the nucleophilic reactivities of Grignard reagents by coordination. This catalytic system has been applied in the efficient synthesis of Citalopram, an effective U.S. FDA-approved antidepressant, and a recyclable version of this catalytic synthesis has also been devised.

Controlled alcohol-carbonyl interconversion by nickel catalysis

All in one pot: A general synthetic platform allows the interconversion of alcohols and carbonyl compounds in a predictable and controlled fashion in one pot. Under the action of a Ni catalyst, PhCl, CsF, and arylboronates, several multistep alcohol-carbonyl interconversions have been achieved with good overall efficiency (see scheme). A one-pot nickel-catalyzed synthesis of flumecinol (a hepatic microsomal enzyme inducer) has also been demonstrated. Copyright

Highly enantioselective arylation of aldehydes and ketones using AlArEt2(THF) as aryl sources

A series of AlArEt2(THF) (Ar = Ph (la), 4-MeC6H 4 (1b), 4-MeOC6H 4 (1c), 4-Me 3SiC6H4 (1d), 2-naphthyl (le)) were synthesized from reactions of AlEt2Br(THF) with ArMgBr. In CDC13 solution, the 1H NMR spectra showed that AlArEt2(THF) compounds exist as a mixture of four species of formulas of AlAr xEt3-x (THF) (x = 0, 1, 2, or 3). AlArEt2(THF) compounds were found to be superior and atom-economic reagents for asymmetric aryl additions to organic carbonyls. Aryl additions of AlArEt2(THF) to aldehydes catalyzed by the titanium(IV) complex of (R)-H8-BINOL were efficient with a short reaction time of 1 h, affording aryl addition products as exclusive or main products in high yields and excellent enantioselectivities of up to 98% ee. Although ethyl additions to aldehydes occurred in minor extent, this study demonstrates that increasing the amount of AlArEt2(THF) from 1.2 to 1.4 or to 1.6 equiv significantly improved the aryl addition products of up to >99%. On the other hand, asymmetric arylations of AlArEt2(THF) to ketones employing a titanium(IV) catalyst of (S)-BINOL produced optically active tertiary alcohols exclusively in excellent enantioselectivities of up to 94% ee.

APPARATUS AND METHOD FOR CARRYING OUT MULTIPLE REACTIONS

The invention provides methods and an apparatus useful for site-isolating reagents or catalysts during chemical reactions. The methods and apparatus are useful for carrying out cascade or domino reactions.