16635-23-7

Upstream product

• 20717-86-6 triisopropoxytitanium(IV) chloride 
• 591-51-5 phenyllithium 
• 108-86-1 bromobenzene 
• 546-68-9 titanium(IV) isopropylate 
• 100-59-4 phenylmagnesium chloride 
• 591-50-4 iodobenzene 
• 100-58-3 phenylmagnesium bromide 

Downstream Products

• 2327-99-3 1-phenylpropadiene 
• 10147-11-2 propargyl benzene 
• 300-57-2 allylbenzene 
• 4544-27-8 (3-methylpenta-1,2-dien-1-yl)benzene 
• 108155-42-6 3-methyl-3-phenyl-1-pentyne 
• 59409-55-1 (1-ethyl-1,2-propadienyl)benzene 
• 33598-21-9 Phenyl-1-pentin-2 
• 27694-86-6 octa-1,2-dien-1-ylbenzene 
• 3412-44-0 (1E)-1,3-diphenylpropene 
• 7693-84-7 (1RS,2RS)-1,2-diphenyl-propan-1-ol 
• 7693-84-7 (1RS,2SR)-1,2-diphenyl-propan-1-ol 
• 15232-96-9 3-phenyl-1-cyclohexene 
• 934-10-1 3-phenylbut-1-ene 
• 1560-06-1 1-phenyl-2-butene 

Relevant academic research and scientific papers

Organotitanium nucleophiles in asymmetric cross-coupling reaction: Stereoconvergent synthesis of chiral α-cf3 thioethers

Asymmetric Ni-catalyzed cross-coupling reactions have become a very attractive tool for the stereoselective construction of valuable organic chiral materials. While various nucleophiles are used in such transformation, organotitanium(IV) has not been used before. Herein we demonstrate, for the first time, that organotitanium species can serve as efficient coupling partners in asymmetric cross-couplings, which have proven to be beneficial, compared to the commonly used organomagnesium and organozinc counterparts. This principle is exemplified by the first asymmetric catalytic synthesis of CF3-substituted thioethers via a Ni-catalyzed stereoconvergent cross-coupling reaction. Thioether moieties and their derivatives are common motifs in many biologically active compounds, and their enantioenriched fluorinated analogs should be of great interest in the search for novel drugs and agrichemicals.

A general palladium-catalyzed cross-coupling of aryl fluorides and organotitanium (IV) reagents

Pd(OAc)2/1-[2-(di-tert-butylphosphanyl)phenyl]-4-methoxy-piperidine was demonstrated to effectively catalyze cross-coupling of aryl fluoride and aryl(alkyl) titanium reagent. Both electron-deficient and electron-rich aryl fluoride can react effectively with nucleophile and provide extensive functional groups tolerance. 2-Arylated product was realized by selective activation of the C–F bond. Graphic abstract: [Figure not available: see fulltext.].

Synthesis of Chiral α-CF3-Substituted Benzhydryls via Cross-Coupling Reaction of Aryltitanates

We describe a highly efficient approach toward α-CF3-substituted benzhydryls thanks to the employment of organotitanium(IV) based nucleophiles. The use of commercially available anesthetic halothane as a cheap fluorinated building block in a sequential one-pot nickel-catalyzed enantioselective cross-coupling reaction of aryl titanates allowed for the synthesis of chiral α-CF3-substituted benzhydryls in good yields and excellent enantioselectivities. Alternatively, α-CF3-benzyl bromides could be employed under similar conditions to obtain the same family of compounds in higher yields and excellent selectivities. A benzhydryl moiety is a common motif in many biologically active compounds, and their enantioenriched fluorinated analogs should be of great interest in the search for novel drugs and agrochemicals.

Silica-Supported Catalyst for Enantioselective Arylation of Aldehydes under Batch and Continuous-Flow Conditions

A silica-supported 3-aryl H8-BINOL-derived titanium catalyst exhibited high performance in the enantioselective arylation of aromatic aldehydes using Grignard and organolithium reagents not only under batch conditions but also under continuous-

Catalytic Enantioselective Arylation and Heteroarylation of Ketones with Organotitanium Reagents Generated In Situ

A practical and useful, catalytic enantioselective method has been developed for the synthesis of tertiary diaryl and aryl heteroaryl carbinols starting from commercially available aromatic ketones and aryl or heteroaryl bromides. In this method, organotitanium reagents are generated in situ from the bromides by lithiation with nBuLi followed by transmetallation of the resulting organolithiums with ClTi(OiPr)3. Treatment of the ketones with the titanium reagents in the presence of (R)-3-(3,5-bistrifluoromehthylphenyl)-1,1′-bi-2-naphthol (BTFP-BINOL) affords the corresponding tertiary alcohols in high enantioselectivities and yields. The reaction can also start with furan and 2-thienyllithium. The method is operationally simple and can be conducted on a 10-mmol scale without any difficulties.

Nickel-catalyzed substitution reactions of propargyl halides with organotitanium reagents

A simple and mild catalytic coupling reaction of propargyl halides with organotitanium reagents is reported. The reaction of propargyl bromide with organo-titanium reagents mediated by NiCl2(2 mol%) and PCy3(4 mol%) in CH2

The Ring Opening of Unsymmetrical Allylic, Benzylic, Propargylic, and Si-Substituted Epoxides by Titanium Acetylides: A Convenient Access to Certain 2-Substituted 3-Butyn-1-ols

Epoxides bearing aryl, alkenyl, alkynyl, and trimethylsilyl substituents react with titanium acetylides at the higher substituted carbon atom exclusively; the 2-substituted 3-butyn-1-ols thus formed are isolated in 33-79percent yield.The dependence of the yield on the solvent, the ratio of the reactands, and their structure is discussed and a reaction mechanism is proposed.

Chemoselective Addition of Organotitanium Reagents to Carbonyl Compounds

The conversion of classical carbanions such as RMgX, RLi, or deprotonated nitriles, sulfones, and carboxylic esters into titanium analogs results in reagents which add chemoselectively to carbonyl compounds in the presence of other functional groups.The standard titanating agent is chlorotriisopropoxytitanium (1).Grignard-type reactions and aldol additions are aldehyde-selective in the presence of ketones.Other functional groups such as alkyl and aryl halides, esters, amides as well as nitro and cyano moieties are tolerated.Discrimination between two aldehydes or two ketones is also possible.Replacing alkoxy ligands by methyl groups at titanium increases reactivity dramatically, relative rates increasing in the series CH3Ti(OCHMe2)3 (CH3)2Ti(OCHMe2)2 (CH3)4Ti.The latter reagent and its zirconium analog methylate sterically hindered and/or enolizable ketones which normally fail to undergo Grignard reactions.The ate complex H2C=CHCH2Ti(OCHMe2)4MgCl (63) is aldehyde-selective, while the amino analog H2C=CHCH2Ti(NMe2)4MgCl (64) adds selectively to ketones in the presence of aldehydes.