306281-87-8

Upstream product

• 402-50-6 1-trifluoromethyl-4-vinyl-benzene 
• 455-19-6 4-Trifluoromethylbenzaldehyde 
• 111991-14-1 2-(4-trifluoromethylphenyl)oxirane 
• 383-53-9 2-bromo-1-[4-(trifluoromethyl)phenyl]ethanone 

Downstream Products

• 306281-94-7 (S)-(+)-1-[p-(trifluoromethyl)phenyl]-2-(triphenylmethoxy)ethanol 
• 306282-10-0 (S)-(+)-4-[p-(trifluoromethyl)phenyl]-1,3-dioxolan-2-one 
• 306281-97-0 (2S,10S)-(+)-2,10-bis[p-(trifluoromethyl)phenyl]-1,11-bis(triphenylmethoxy)-3,6,9-trioxaundecane 
• 306282-06-4 (5S,13S)-(+)-21-hydroxy-19-methoxy-5,13-bis[p-(trifluoromethyl)phenyl]-3,6,9,12,15-pentaoxabicyclo[15.3.1]henicosa-1⁽²¹⁾,17,19-triene 
• 306282-03-1 (5S,13S)-(+)-19,21-dimethoxy-5,13-bis[p-(trifluoromethyl)phenyl]-3,6,9,12,15-pentaoxabicyclo[15.3.1]henicosa-1⁽²¹⁾,17,19-triene 
• 306282-09-7 (5S,13S)-5,13-Bis-(4-trifluoromethyl-phenyl)-3,6,9,12,15-pentaoxa-bicyclo[15.3.1]henicosa-1⁽²⁰⁾,17-diene-19,21-dione 
• 306282-00-8 (2S,10S)-(+)-2,10-bis[p-(trifluoromethyl)phenyl]-3,6,9-trioxaundecane-1,11-diol 
• 306282-11-1 (R)-(-)-2-azido-2-[p-(trifluoromethyl)phenyl]ethanol 
• 306281-86-7 (R)-(-)-2-amino-2-[p-(trifluoromethyl)phenyl]ethanol 

Relevant academic research and scientific papers

Enantioselective trans-dihydroxylation of aryl olefins by cascade biocatalysis with recombinant escherichia coli coexpressing monooxygenase and epoxide hydrolase

Cascade biocatalysis via intracellular epoxidation and hydrolysis was developed as a green and efficient method for enantioselective dihydroxylation of aryl olefins to prepare chiral vicinal diols in high ee and high yield. Escherichia coli (SSP1) coexpressing styrene monooxygenase (SMO) and epoxide hydrolase SpEH was developed as a simple and efficient biocatalyst for S-enantioselective dihydroxylation of terminal aryl olefins 1a-15a to give (S)-vicinal diols 1c-15c in high ee (97.5-98.6% for 10 diols; 92.2-93.9% for 3 diols) and high yield (91-99% for 6 diols; 86-88% for 2 diols; 67% for 3 diols). Combining SMO and epoxide hydrolase StEH showing complementary regioselectivity to SpEH as a biocatalyst for the cascade biocatalysis gave rise to R-enantioselective dihydroxylation of aryl olefins, being the first example of this kind of reversing the overall enantioselectivity of cascade biocatalysis. E. coli (SST1) coexpressing SMO and StEH was also engineered as a green and efficient biocatalyst for R-dihydroxylation of terminal aryl olefins 1a-15a to give (R)-vicinal diols 1c-15c in high ee (94.2-98.2% for 7 diols; 84.2-89.9% for 6 diols) and high yield (90-99% for 6 diols; 85-89% for 5 diols; 65% for 1 diol). E. coli (SSP1) and E. coli (SST1) catalyzed the trans-dihydroxylation of trans-aryl olefin 16a and cis-aryl olefin 17a with excellent and complementary stereoselectivity, giving each of the four stereoisomers of 1-phenyl-1,2- propanediol 16c in high ee and de, respectively. Both strains catalyzed the trans-dihydroxylation of aryl cyclic olefins 18a and 19a to afford the same trans-cyclic diols (1R,2R)-18c and (1R,2R)-19c, respectively, in excellent ee and de. This type of cascade biocatalysis provides a tool that is complementary to Sharpless dihydroxylation, accepting cis-alkene and offering enantioselective trans-dihydroxylation.

Reprogramming Epoxide Hydrolase to Improve Enantioconvergence in Hydrolysis of Styrene Oxide Scaffolds

Enantioconvergent hydrolysis by epoxide hydrolase is a promising method for the synthesis of important vicinal diols. However, the poor regioselectivity of the naturally occurring enzymes results in low enantioconvergence in the enzymatic hydrolysis of styrene oxides. Herein, modulated residue No. 263 was redesigned based on structural information and a smart variant library was constructed by site-directed modification using an “optimized amino acid alphabet” to improve the regioselectivity of epoxide hydrolase from Vigna radiata (VrEH2). The regioselectivity coefficient (r) of variant M263Q for the R-isomer of meta-substituted styrene oxides was improved 40–63-fold, and variant M263V also exhibited higher regioselectivity towards the R-isomer of para-substituted styrene oxides compared with the wild type, which resulted in improved enantioconvergence in hydrolysis of styrene oxide scaffolds. Structural insight showed the crucial role of residue No. 263 in modulating the substrate binding conformation by altering the binding surroundings. Furthermore, increased differences in the attacking distance between nucleophilic residue Asp101 and the two carbon atoms of the epoxide ring provided evidence for improved regioselectivity. Several high-value vicinal diols were readily synthesized (>88% yield, 90%–98% ee) by enantioconvergent hydrolysis using the reprogrammed variants. These findings provide a successful strategy for enhancing the enantioconvergence of native epoxide hydrolases through key single-site mutation and more powerful enzyme tools for the enantioconvergent hydrolysis of styrene oxide scaffolds into single (R)-enantiomers of chiral vicinal diols. (Figure presented.).

Chiral Ion-Pair Organocatalyst-Promoted Efficient Enantio-selective Reduction of α-Hydroxy Ketones

The enantioselective reduction of α-hydroxy ketones with catecholborane has been developed employing 5 mol% of an 1,1′-bi-2-naphthol (BINOL)-derived ion-pair organocatalyst. This methodology provides a straightforward access to the corresponding aromatic 1,2-diols in high yields (up to 90%) with excellent enantioselectivities (up to 97%). Furthermore, the α-amino ketones also could be reduced with moderate ee values under mild reaction condition. (Figure presented.).

Structurally Defined Molecular Hypervalent Iodine Catalysts for Intermolecular Enantioselective Reactions

Molecular structures of the most prominent chiral non-racemic hypervalent iodine(III) reagents to date have been elucidated for the first time. The formation of a chirally induced supramolecular scaffold based on a selective hydrogen-bonding arrangement provides an explanation for the consistently high asymmetric induction with these reagents. As an exploratory example, their scope as chiral catalysts was extended to the enantioselective dioxygenation of alkenes. A series of terminal styrenes are converted into the corresponding vicinal diacetoxylation products under mild conditions and provide the proof of principle for a truly intermolecular asymmetric alkene oxidation under iodine(I/III) catalysis.

Production Of Enantiopure alpha-Hydroxy Carboxylic Acids From Alkenes By Cascade Biocatalysis

The invention provides compositions comprising an alkene epoxidase and a selective epoxide hydrolase, such as a recombinant microorganism comprising a first heterologous nucleic acid encoding an alkene epoxidase and a second heterologous nucleic acid encoding a selective epoxide hydrolase. Exemplary alkene epoxidases include StyAB, while exemplary selective epoxide hydrolases include epoxide hydrolases from Sphingomonas, Solanum tuberosum, or Aspergillus. The invention also provides non-toxic methods of making enantiomerically pure vicinal diols or enantiomerically pure alpha-hydroxy carboxylic acids using these compositions and microorganisms.

Enantioselective Vicinal Diacetoxylation of Alkenes under Chiral Iodine(III) Catalysis

A procedure for the intermolecular enantioselective dioxygenation of alkenes under iodine(III) catalysis has been developed. This protocol employs Selectfluor as the terminal oxidant together with a defined C 2-symmetric aryl iodide as the organocatalyst. This enantioselective reaction proceeds under mild conditions and converts a series of terminal and internal styrenes into the corresponding vicinal diacetoxylation products with up to 96% ee.

Scope and mechanism of the Pt-catalyzed enantioselective diboration of monosubstituted alkenes

The Pt-catalyzed enantioselective diboration of terminal alkenes can be accomplished in an enantioselective fashion in the presence of chiral phosphonite ligands. Optimal procedures and the substrate scope of this transformation are fully investigated. Reaction progress kinetic analysis and kinetic isotope effects suggest that the stereodefining step in the catalytic cycle is olefin migratory insertion into a Pt-B bond. Density functional theory analysis, combined with other experimental data, suggests that the insertion reaction positions platinum at the internal carbon of the substrate. A stereochemical model for this reaction is advanced that is in line both with these features and with the crystal structure of a Pt-ligand complex.

Synthesis and catalytic activity of TentaGel-supported asymmetric dihydroxylation (DHQ)2PHAL ligand

An efficient scheme for the synthesis and catalytic activity of TentaGel-supported Sharpless's (DHQ)2PHAL dihydroxylation ligand is described. Crown Copyright

Enzymatic transformations 63. High-concentration two liquid-liquid phase Aspergillus niger Epoxide hydrolase-catalysed resolution: Application to trifluoromethyl-substituted aromatic epoxides

The aim of this work was to perform different studies allowing us to improve the methodology we had previously described to realise the Aspergillus niger epoxide hydrolase-catalysed resolution of eight trifluoromethyl- substituted styrene oxide derivative

Enzymatic transformations; 61. Preparation of enantiopure trifluoromethyl-substituted aromatic epoxides and vicinal diols using the Aspergillus niger epoxide hydrolase-catalysed resolution

The resolution of eight differently substituted trifluoromethylstyrene oxide derivatives was explored using the Aspergillus niger epoxide hydrolase. The obtained results indicate that all (but one) epoxides were efficiently processed by this enzyme, under