33863-75-1

Upstream product

• 100-52-7 benzaldehyde 
• 107-14-2 chloroacetonitrile 
• 1885-38-7 cinnamic nitrile 
• 24840-05-9 (Z)-cinnamonitrile 
• 33863-75-1 (±)-cis-phenyloxirane-2-carbonitrile 
• 28000-59-1 α,α-diiodotoluene 
• 3252-43-5 dibromoacetonitrile 

Downstream Products

• 73627-97-1 3-hydroxy-3-phenylpropanenitrile 
• 79963-86-3 1-cyano 2-fluoro-2-phenylethanol 
• 83144-21-2 Acetic acid (E)-1-cyano-2-phenyl-vinyl ester 
• 343953-79-7 2,2-Dimethyl-5-phenyl-[1,3]dioxolane-4-carbonitrile 
• 19190-80-8 cis-methyl 2,3-epoxy-3-phenylpropanoate 
• 124649-67-8 methyl (2S,3R)-3-phenyl-2,3-dihydroxypropanoate 
• 33863-75-1 cis-3-phenyloxirane-2-carbonitrile 
• 133520-53-3 2,3-Dihydroxy-3-phenylpropannitril 
• 133520-56-6 2,2-Dimethyl-5-phenyl-1,3-dioxolan-4-carbonitril 
• 214194-15-7 (4S,5R)-2,2-dimethyl-5-phenyl-[1,3]dioxolane-4-carboxylic acid methyl ester 
• 7309-55-9 N-benzoyl-(2R^*,3S^*)-3-phenylisoserine 

Relevant academic research and scientific papers

Concerning the reactivity of dioxiranes. Observations from experiments and theory

The challenging hypothesis of a biphilic (i.e., electrophilic vs nucleophilic) character for dioxirane reactivity, which envisages that electron-poor alkenes are attacked by dioxiranes in a nucleophilic fashion, could not be sustained experimentally. Rate data, which estimate Hammett rho values for the epoxidation of 3- or 4-substituted cinnamonitriles X·Ph-CH=CH-CN, unequivocally allow one to establish that dioxiranes epoxidize electrophilically even alkenes carrying electron-withdrawing-groups. The greater propensity of methyl(trifluoromethyl) dioxirane TFDO (1b) to act as an electrophilic oxidant with respect to dimethyldioxirane DDO (1a) parallels the cathode reduction potentials for the two dioxiranes, as measured by cyclic voltammetry. A simple FMO approach for alkene epoxidation is helpful to conceive a likely rationale for the greater oxidizing power of TFDO as compared to DDO.

Insertion of metallated epoxynitriles into organozirconocene chlorides. A convergent synthesis of 2-cyano-1,3-dienes

Lithiated epoxynitriles insert efficiently into alkenyizirconocene chlorides via a 1,2-metallate rearrangement to form intermediates which eliminate Cp2Zr(Cl)O- to afford substituted 2-cyano-1,3-dienes. (C) 2000 Elsevier Science Ltd.

BF3·OEt2-promoted tandem Meinwald rearrangement and nucleophilic substitution of oxiranecarbonitriles

Tandem Meinwald rearrangement and nucleophilic substitution of oxiranenitriles was realized. Arylacetic acid derivatives were readily synthesized from 3-aryloxirane-2-carbonitriles with amines, alcohols, or water in the presence of boron trifluoride under microwave irradiation, and the designed synthetic strategy includes introducing a cyano leaving group into arylepoxides and capturing the in situ generated toxic cyanide with boron trifluoride, making the reaction efficient, safe, and environmentally benign. The reaction occurs through an acid-promoted Meinwald rearrangement, producing arylacetyl cyanides, followed by an addition-elimination process with nitrogen or oxygen-containing nucleophilic amines, alcohols or water. The current method provides a new application of the tandem Meinwald rearrangement.

BF 3 ·oEt 2 -Catalyzed Synthesis of anti -β-(N -Arylamino)-α-hydroxynitriles by Regio- And Diastereospecific Ring Opening of 3-Aryloxirane-2-carbonitriles with Anilines

A safe and convenient synthetic method to anti -β-(N -arylamino)-α-hydroxynitriles from 3-aryloxirane-2-carbonitriles and anilines was developed under the catalysis of BF 3 ·OEt 2 in ethanol. In this method, BF 3 ·OEt 2 first reacts with ethanol to produce the true catalyst of super- acid H[B(OEt)F 3], followed by an acid-catalyzed regio- and diastereospecific ring opening of oxirane-2-carbonitriles with anilines, generating anti -β-(N -arylamino)-α-hydroxynitriles. The method features the advantages of non-metal catalysis, short reaction times, and easy operation, and uses an environmentally friendly solvent.

Metal-free and regiospecific synthesis of 3-arylindoles

A convenient, metal-free, and organic acid-base promoted synthetic method to prepare 3-arylindoles from 3-aryloxirane-2-carbonitriles and arylhydrazine hydrochlorides has been developed. In the reaction, the organic acid catalyzes a tandem nucleophilic ri

Oxygenophilic Lewis Acid Promoted Synthesis of 2-Arylindoles from Anilines and Cyanoepoxides in Alcohol

A convenient synthetic method to indoles from anilines and cyanoepoxides was developed under the catalysis of BF3·OEt2 or AlCl3 in alcohols. The reaction involves a tandem reaction of the regiospecific ring-opening of cyanoepoxides with anilines, elimination of cyanide, intramolecular aromatic electrophilic substitution, and water elimination. The Lewis acid generated protic acid is an efficient catalyst. The method features readily accessible starting materials, wide substrate scope, transition-metal-free environment, and regiospecificity in the ring-opening of cyanoepoxides.

ALPHA-HYDROXY-BETA-AZIDO-TETRAZOLES

Alpha-hydroxy-beta-azido tetrazole compounds of formula (I): a process for manufacturing alpha-hydroxy-beta-azido tetrazoles of formula (I), and their use for synthesizing new compounds, e.g. in “click” chemistry.

An investigation of nitrile transforming enzymes in the chemo-enzymatic synthesis of the taxol sidechain

Paclitaxel (taxol) is an antimicrotubule agent widely used in the treatment of cancer. Taxol is prepared in a semisynthetic route by coupling the N-benzoyl-(2R,3S)-3-phenylisoserine sidechain to the baccatin III core structure. Precursors of the taxol sidechain have previously been prepared in chemoenzymatic approaches using acylases, lipases, and reductases, mostly featuring the enantioselective, enzymatic step early in the reaction pathway. Here, nitrile hydrolysing enzymes, namely nitrile hydratases and nitrilases, are investigated for the enzymatic hydrolysis of two different sidechain precursors. Both sidechain precursors, an openchain α-hydroxy-β-amino nitrile and a cyanodihydrooxazole, are suitable for coupling to baccatin III directly after the enzymatic step. An extensive set of nitrilases and nitrile hydratases was screened towards their activity and selectivity in the hydrolysis of two taxol sidechain precursors and their epimers. A number of nitrilases and nitrile hydratases converted both sidechain precursors and their epimers.

Enantioselective bio-hydrolysis of various racemic and meso aromatic epoxides using the recombinant epoxide hydrolase Kau2

Abstract Epoxide hydrolase Kau2 overexpressed in Escherichia coli RE3 has been tested with ten different racemic and meso α,β-disubstituted aromatic epoxides. Some of the tested substrates were bi-functional, and most of them are very useful building blocks in synthetic chemistry applications. As a general trend Kau2 proved to be an extremely enantioselective biocatalyst, the diol products and remaining epoxides of the bioconversions being obtained - with two exceptions - in nearly enantiomerically pure form. Furthermore, the reaction times were usually very short (around 1 h, except when stilbene oxides were used), and the use of organic co-solvents was well tolerated, enabling very high substrate concentrations (up to 75 g/L) to be reached. Even extremely sterically demanding epoxides such as cis- and trans-stilbene oxides were transformed on a reasonable time scale. All reactions were successfully conducted on a 1 g preparative scale, generating diol- and epoxide-based chiral synthons with very high enantiomeric excesses and isolated yields close to the theoretical maximum. Thus we have here demonstrated the usefulness and versatility of lyophilized Escherichia coli cells expressing Kau2 epoxide hydrolase as a highly enantioselective biocatalyst for accessing very valuable optically pure aromatic epoxides and diols through kinetic resolution of racemates or desymmetrization of meso epoxides.

Biotransformations of 2,3-epoxy-3-arylpropanenitriles by Debaryomyces hansenii and Mortierella isabellina cells

Biotransformations of five substituted cis- and trans-oxiranecarbonitriles with Mortierella isabellina DSM 1414, a microbial whole-cell catalyst producing epoxide hydrolases, were investigated. The reactions were stopped when the conversion of the substrates reached 50%. They yielded the appropriate optically active dihydroxycarbonitriles and oxiranecarbonitriles in low enantiomeric purity. Kinetic resolution of rac-syn-2,3-dihydroxy-3-arylpropanenitriles by lipase catalyzed acetylation yielded almost enantiomerically pure (-)-dihydroxynitriles and mixtures of regioisomers of monoacetylated diols. Another microorganism, Debaryomyces hansenii DSM 3428, was used as a source of nitrile hydratases in the kinetic resolution of oxiranecarbonitriles. Only two trans-configured compounds were transformed into the corresponding oxiranecarboxamides.