77256-62-3

Upstream product

• 98-85-1 1-Phenylethanol 
• 49623-71-4 2,4,6-triisopropylbenzoic acid 
• 57199-00-5 2,4,6-triisopropylbenzoyl chloride 
• 100-41-4 ethylbenzene 
• 21524-34-5 2,4,6-triisopropyl-1-bromobenzene 
• 77256-41-8 benzyl 2,4,6-triisopropylbenzoate 
• 74-88-4 methyl iodide 

Downstream Products

• 77256-83-8 2-(2-phenylpropyl) 2,4,6-triisopropylbenzoate 
• 173031-59-9 Methyl 2-phenyl-2-(2,4,6-triisopropylbenzyloxy)propionate 
• 173031-63-5 2-Phenyl-2-(2,4,6-triisopropylbenzoyloxy)-1-propanol 
• 2406-22-6 (R)-1-phenyl-1,2-ethanediol 
• 2406-22-6 (2S)-2-phenylpropane-1,2-diol 
• 4217-66-7 1,2-dihydroxy-2-phenylpropane 

Relevant academic research and scientific papers

The two alternative rate-determining steps in benzylic lithiation reactions of esters and Carbamates

Lithiation reactions of tertiary benzylic esters and carbamates have been studied. Kinetic methodology revealed that a two-step reaction pathway should be considered for these reactions, where either the lithium precomplexation and/or the proton transfer

Esterification of the Primary Benzylic C-H Bonds with Carboxylic Acids Catalyzed by Ionic Iron(III) Complexes Containing an Imidazolinium Cation

The first iron-catalyzed esterification of the primary benzylic C-H bonds with carboxylic acids using di-tert-butyl peroxide as an oxidant is achieved by novel ionic iron(III) complexes containing an imidazolinium cation. The use of well-defined, air-stable, and available iron(III) complex in a 5 mol % loading and readily available starting materials with a broad generality and outstanding sterically hindered tolerance renders this methodology a useful alternative to other protocols that are typically employed for the synthesis of benzyl esters.

Chiral Carbanions, 1. - Configurational Stability and Reactions of α-Acyloxy-Substituted α-Methylbenzyllithium Compounds

Racemic and optically active 1-phenylethyl esters of pivalic, (-)-camphanic and 2,4,6-triisopropylbenzoic acid were prepared.The esters 7a of pivalic acid were deprotonated with lithium 2,2,6,6-tetramethylpiperidide (Li-TMP) to form α-oxy-α-methylbenzyllithium compounds which are partly configurationally stable prior to acylation with starting material.Camphanic ester (-)-7b cannot be deprotonated by Li-TMP and t-BuLi is added to the ester function to afford ketone (-)-12a. 1-Phenylethyl 2,4,6-triisopropylbenzoates 16 were transformed within minutes to carbanions 19 by using s-BuLi/TMEDA in THF, hexane, toluene and s-BuLi without TMEDA in toluene/20percent diethyl ether at -78 deg C.The carbanions are configurationally stable only in toluene/20percent diethyl ether and racemise partly in the other solvents.They react with a variety of electrophiles with either retention or inversion (Me3SnCl) of configuration.Carbanions 19 rearrange on warming to -20 deg C to hydroxy ketone 24 with racemisation. - Keywords: Esters, 1-phenylethyl; Carbanions, α-methyl-α-oxybenzyl, configurational stability; Ester-hydroxy ketone rearrangement

Dipole-Stabilized Carbanions from Esters: α-Oxo Lithiations of 2,6-Substituted Benzoates of Primary Alcohols

The synthetic utility of dipole-stabilized carbanions from esters is illustrated by the preparations, α-oxo lithiations, electrophilic substitutions, and cleavages of the 2,4,6-triisopropylbenzoates and the 2,6-bis(dimethylamino)-3,5-diisopropylbenzoates of primary alcohols, 2 and 3, respectively.Typical electrophiles used in this methodology include primary alkyl halides, aldehydes, ketones, trimethylsilyl chloride, and tri-n-butyltin chloride.Cleavages of the substituted esters of 2 are accomplished with lithium aluminum hydride while hydrolyses of derivatives of3 can be achieved under acidic conditions.The 2,6-substitutions of 2 and 3 are considered to enforce orthogonality of the carbonyl group and the phenyl ring and thereby to inhibit addition to the carbonyl by the organolithium base used for the metalation by placing the substituents in the trajectory for nucleophilic addition along the LUMO of the carbonyl.The acidic hydrolysis of 3 under conditions where 2 is stable is attributed to protonation of the dimethylamino group which provides subsequent assistance for nucleophilic addition.These metalations provide the key steps in the preparation of secondary α-lithio alcohol synthetic equivalents from primary alcohols.Lithiation of 1'-methylbenzyl 2,4,6-triisopropylbenzoate proceeds α to oxygen as expected, but attempts to prepare analogous unactivated tertiary α-lithio esters were unsuccessful.The lithiation of 2'-methoxyethyl 2,4,6-triisopropylbenzoate is followed by elimination of methoxide and α-oxo metalation of the resulting vinyl ester.Lithiation of allyl 2,4,6-triisopropylbenzoate provides 1-(2,4,6-triisopropylphenyl)-1,2-butanedione by rearrangement.