2901-11-3

Usage

InChI:InChI=1/C13H18O2/c1-10(11-8-6-5-7-9-11)12(14)15-13(2,3)4/h5-10H,1-4H3

Upstream product

• 108-86-1 bromobenzene 
• 20487-40-5 tert-butyl propionate 
• 25145-43-1 2-phenylpropionyl chloride 
• 75-65-0 tert-butyl alcohol 
• 108-90-7 chlorobenzene 
• 492-37-5 hydratropic acid 
• 93891-72-6 CH₃CH(ZnBr)CO₂C(CH₃)3*OC₄H₈ 
• 100-46-9 benzylamine 
• 101-41-7 benzeneacetic acid methyl ester 
• 540-88-5 acetic acid tert-butyl ester 
• 16537-09-0 t-butyl phenylacetate 
• 74-88-4 methyl iodide 
• 201230-82-2 carbon monoxide 
• 585-71-7 (1-bromoethyl)benzne 

Downstream Products

• 648424-78-6 (R)-tert-butyl 2-hydroxy-2-phenylpropanoate 
• 885316-13-2 (S)-tert-butyl 2-hydroxy-2-phenylpropanoate 
• 31508-44-8 2-phenylpropionic acid methyl ester 
• 25145-43-1 2-phenylpropionyl chloride 
• 7782-24-3 (S)-2-Phenylpropionic acid 
• 7782-26-5 (R)-2-Phenylpropionic acid 
• 1123-85-9 (RS)-2-phenyl-1-propanol 
• 2901-24-8 tert-butyl 2-methyl-2-phenylpropionate 
• 117606-75-4 (S)-2-Methyl-3-oxo-2-phenyl-butyric acid tert-butyl ester 
• 114577-81-0 (E)-2-Methyl-4-nitro-2-phenyl-but-3-enoic acid tert-butyl ester 

Relevant academic research and scientific papers

Isothiourea-Catalyzed Acylative Kinetic Resolution of Tertiary α-Hydroxy Esters

A highly enantioselective isothiourea-catalyzed acylative kinetic resolution (KR) of acyclic tertiary alcohols has been developed. Selectivity factors of up to 200 were achieved for the KR of tertiary alcohols bearing an adjacent ester substituent, with both reaction conversion and enantioselectivity found to be sensitive to the steric and electronic environment at the stereogenic tertiary carbinol centre. For more sterically congested alcohols, the use of a recently-developed isoselenourea catalyst was optimal, with equivalent enantioselectivity but higher conversion achieved in comparison to the isothiourea HyperBTM. Diastereomeric acylation transition state models are proposed to rationalize the origins of enantiodiscrimination in this process. This KR procedure was also translated to a continuous-flow process using a polymer-supported variant of the catalyst.

Palladium-catalyzed α-arylation of zinc enolates of esters: Reaction conditions and substrate scope

The intermolecular α-arylation of esters by palladium-catalyzed coupling of aryl bromides with zinc enolates of esters is reported. Reactions of three different types of zinc enolates have been developed. α-Arylation of esters occurs in high yields with i

Use of a robust dehydrogenase from an archael hyperthermophile in asymmetric catalysis-dynamic reductive kinetic resolution entry into (s)-profens

Described is an efficient heterologous expression system for Sulfolobus solfataricus ADH-10 (Alcohol Dehydrogenase isozyme 10) and its use in the dynamic reductive kinetic resolution (DYRKR) of 2-arylpropanal (Profen-type) substrates. Importantly, among the 12 aldehydes tested, a general preference for the (S)-antipode was observed, with high ee's for substrates corresponding to the NSAIDs (nonsteroidal anti-inflammatory drugs) naproxen, ibuprofen, flurbiprofen, ketoprofen, and fenoprofen. To our knowledge, this is the first application of a dehydrogenase from this Sulfolobus hyperthermophile to asymmetric synthesis and the first example of a DYRKR with such an enzyme. The requisite aldehydes are generated by Buchwald-Hartwig-type Pd(0)-mediated α-arylation of tert-butyl propionate. This is followed by reduction to the aldehyde in one [lithium diisobutyl tert-butoxyaluminum hydride (LDBBA)] or two steps [LAH/Dess-Martin periodinane]. Treatment of the profenal substrates with SsADH in 5% EtOH/phosphate buffer, pH 9, with catalytic NADH at 80 °C leads to efficient DYRKR, with ee's exceeding 90% for 9 aryl side chains, including those of the aforementioned NSAIDs. An in silico model, consistent with the observed broad side chain tolerance, is presented. Importantly, the SsADH-10 enzyme could be conveniently recycled by exploiting the differential solubility of the organic substrate/product at 80 °C and at rt. Pleasingly, SsADH-10 could be taken through several thermal cycles, without erosion of ee, suggesting this as a generalizable approach to enzyme recycling for hyperthermophilic enzymes. Moreover, the robustness of this hyperthermophilic DH, in terms of both catalytic activity and stereochemical fidelity, speaks for greater examination of such archaeal enzymes in asymmetric synthesis.

Kinetic resolution of racemic carboxylic acids by an L-histidine-derived sulfonamide-induced enantioselective esterification reaction

(Chemical Equation Presented) The direct and catalytic kinetic resolution of racemic carboxylic acids bearing a Bronsted base such as O-protected α-hydroxy carboxylic acids and N-protected α-amino acids has been accomplished through an L-histidine-derived sulfonamide-induced enantioselective esterification reaction with tert-butyl alcohol for the first time. Highly asymmetric induction [S(kfast/kslow) = up to 56] has been achieved under the equilibrium between a chiral catalyst and two diastereomeric acylammonium salts through an intramolecular hydrogen-bonding interaction.

Palladium-catalyzed-arylattion of esters With chloroarenes

Palladium-catalyzed α-arylations of esters with chloroarenes are reported. The reactions of chloroarenes with the sodium enolates of tert-butyl propionate and methyl isobutyrate occur in high yields with 0.2-1 mol % of {[P(f-Bu)3]PdBr}2/s

Efficient synthesis of α-aryl esters by room-temperature palladium-catalyzed coupling of aryl halides with ester enolates

A catalytic amount of Pd(dba)2 ligated by either carbene precursor N,N′-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolium (1) or P(t-Bu)3 mediated the coupling of aryl halides and ester enolates to produce α-aryl esters in high yields at room temperature. The reaction was highly tolerant of functionalities and substitution patterns on the aryl halide. Improved protocols for the selective monoarylation of tert-butyl acetate and the efficient arylation of α,α-disubstituted esters were developed with LiNCy2 as base and P(t-Bu)3 as ligand. In addition, tert-butyl esters, such as those of Naproxen and Flurbiprofen, were prepared from tert-butyl propionate and aryl bromides in high yields in the presence of Pd(dba)2 and the hindered, saturated heterocyclic carbene ligand precursor.

Homolytic Reactions of Ligated Boranes. Part 16. Enantioselective Hydrogen-atom Abstraction by Chiral Amine-Boryl Radicals: Catalytic Kinetic Resolution of Esters and of Camphor

UV irradiation of an oxirane solution containing di-tert-butyl peroxide, an amine-alkylborane complex (in which the B-alkyl group is optically active) and a racemic ester or camphor as substrate, gives rise initially to the tert-butoxyl radical which rapidly abstracts hydrogen from the complex to form an optically active amine-boryl radical.The amine-boryl radical then abstracts hydrogen enantioselectively from a C-H group α to the carbonyl group in the substrate to regenerate the amine-alkylborane.This abstraction reaction has been used to bring about catalytic kinetic resolution of the substrate, using the bis(isopinocampheylborane) complex of N,N,N',N'-tetramethylethylenediamine and some of its derivatives as catalysts.After partial consumption of the substrate, the amount remaining and its enantiomeric excess (ee) have been used to derive enantioselectivity constants for hydrogen-atom abstraction.Enantioselectivity varies considerably with the structure of the substrate.The highest selectivity was observed for hydrogen abstraction from dimethyl 2,2-dimethyl-1,3-dioxolane-trans-4,5-dicarboxylate, when after 75percent consumption of initially-racemic ester at -90 deg C, the residual substrate showed an ee of 97percent.A transition-state model is proposed to account for the observed enantioselectivities.

A Study of the Ferrous Ion-initiated SRN1 Reactions of Halogenoarenes with tert-Butyl Acetate and N-Acylmorpholine Enolates

A detailed preparative study is reported of the ferrous ion-initiated SRN1 reactions of a range of halogenoarenes with the sodium enolates of tert-butyl acetate, n-acetylmorpholine and a number of higher N-acylmorpholines.Smooth and rapid substitution occurs in many cases, and good to excellent yields were obtained of arylacetic esters or acids, arylacetamides and arylalkanamides.The broad scope and limitations of the process have been defined, and the possible role of the ferrous ion is discussed.

Transesterification of methyl arylacetates wtih lithium alkoxides

A series of methyl arylacetates were transesterified in excellent yields using lithium alkoxides derived from primary, secondary, and tertiary aliphatic alcohols, benzyl alcohols, and allyl alcohol.