138769-96-7

Basic information

• Product Name: (+)-CIS-2(R),3(S)-2,3-DIHYDROXY-2,3-DIHYDROBENZONITRILE
• Synonyms: CIS-(1S,2R)-3-CYANO-3,5-CYCLOHEXADIENE-1,2- DIOL;(+)-CIS-2(R),3(S)-2,3-DIHYDROXY-2,3-DIHYDROBENZONITRILE
• CAS NO: 138769-96-7
• Molecular Formula: C₇H₇NO₂
• Molecular Weight: 137.14
• Mol File: 138769-96-7.mol

Chemical Properties

• Boiling Point: 341.2±42.0 °C(Predicted)
• Appearance: /
• Density: 1.33±0.1 g/cm3(Predicted)
• PKA: 12.20±0.60(Predicted)
• CAS DataBase Reference: (+)-CIS-2(R),3(S)-2,3-DIHYDROXY-2,3-DIHYDROBENZONITRILE(CAS DataBase Reference)
• NIST Chemistry Reference: (+)-CIS-2(R),3(S)-2,3-DIHYDROXY-2,3-DIHYDROBENZONITRILE(138769-96-7)
• EPA Substance Registry System: (+)-CIS-2(R),3(S)-2,3-DIHYDROXY-2,3-DIHYDROBENZONITRILE(138769-96-7)

Safety Data

• Hazardous Substances Data: 138769-96-7(Hazardous Substances Data)

Usage

Uses

Used in Organic Synthesis:
(+)-CIS-2(R),3(S)-2,3-DIHYDROXY-2,3-DIHYDROBENZONITRILE is used as a building block in organic synthesis for the creation of various chemical compounds.
Used in Pharmaceutical Manufacturing:
(+)-CIS-2(R),3(S)-2,3-DIHYDROXY-2,3-DIHYDROBENZONITRILE is used as an intermediate in the production of pharmaceuticals, contributing to the development of new drugs.
Used in Agrochemical Production:
(+)-CIS-2(R),3(S)-2,3-DIHYDROXY-2,3-DIHYDROBENZONITRILE is utilized as an intermediate in the manufacture of agrochemicals, aiding in the development of agricultural products.
Used in Medicine:
(+)-CIS-2(R),3(S)-2,3-DIHYDROXY-2,3-DIHYDROBENZONITRILE is used as a potential therapeutic agent in medicine due to its ability to interact with biological systems.
Used in Biotechnology:
(+)-CIS-2(R),3(S)-2,3-DIHYDROXY-2,3-DIHYDROBENZONITRILE is employed in biotechnology for its potential applications in various biological processes and systems.

Upstream product

• 100-47-0 benzonitrile 
• 622-79-7 benzyl azide 
• 591-50-4 iodobenzene 
• 2179-92-2 tri-n-butyltin cyanide 
• 138769-92-3 cis-(1S,2S)-1,2-dihydroxy-3-iodocyclohexa-3,5-diene 

Downstream Products

• 150767-96-7 (1R,6S)-2-cyano-8,8-dimethyl-7,9-dioxabicyclo<4.3.0>nona-2,4-diene 
• 873-62-1 m-cyanophenol 
• 1227264-37-0 (3S,4S,5R,6R)-3,4,5,6-tetrahydroxy-1-cyclohexene-1-carbonitrile 
• 1228121-54-7 (1S,2R,3S)-3-cyanocyclohexane-1,2-diol 
• 1228121-57-0 (1S,2R,3R)-3-cyanocyclohexane-1,2-diol 
• 176965-84-7 Acetic acid (1R,2R,5R,6S)-2,5,6-triacetoxy-3-cyano-cyclohex-3-enyl ester 
• 177186-14-0 Acetic acid (1R,2R,5S,6R)-2,5,6-triacetoxy-3-cyano-cyclohex-3-enyl ester 
• 176965-85-8 Acetic acid (1R,2S,3R,5S,6R)-2,3,6-triacetoxy-5-cyano-cyclohexyl ester 
• 176965-83-6 (3R,4S,5R,6R)-3,4,5,6-Tetrahydroxy-cyclohex-1-enecarbonitrile 
• 67984-81-0 2,3-dihydroxybenzonitrile 

Relevant articles and documents

Recombinant chlorobenzene dioxygenase from Pseudomonas sp. P51: A biocatalyst for regioselective oxidation of aromatic nitriles

An efficient biocatalyst was developed for the cis-dihydroxylation of aromatic nitriles. The chlorobenzene dioxygenase (CDO) genes of Pseudomonas sp. strain P51 were cloned under the strict control of the Palk promoter of Pseudomonas putida GPo1. Escherichia coli JM101 cells carrying the resulting plasmid pTEZ30 were used for the biotransformation of benzonitrile in a 2-L stirred tank bioreactor. Use of a stable expression system resulted in an average specific activity and an average volumetric productivity of 1.47 U/g cdw and 120 mg of product/h/L, respectively. The values represent a three-fold increase compared to the results of the similar biotransformations with E. coli JM101 (pTCB144) where the genes of CDO were expressed under the control of lac promoter. The productivity of the cis-dihydroxylation process was limited by product toxicity. Removal of the products at toxic concentrations by means of an external charcoal column resulted in an additional increase in product concentration by 43%. E. coli JM101 (pTEZ30) was further used for the regio- and stereospecific dihydroxylations of various monosubstituted benzonitriles, benzyl cyanide, and cinnamonitrile. Biotransformations resulted in products with 42.9-97.1% enantiomeric excess. Initial enzymatic activities and isolated yields were obtained in the range of 1.7-4.7 U/g cdw and of 3-62%, respectively.

Toluene Dioxygenase-Catalysed Oxidation of Benzyl Azide to Benzonitrile: Mechanistic Insights for an Unprecedented Enzymatic Transformation

Enzymatic dioxygenation of benzyl azide by toluene dioxygenase (TDO) produces significant amounts of the cis-cyclohexadienediol derived from benzonitrile, along with the expected azido diols. We demonstrate that TDO catalyses the oxidation of benzyl azide to benzonitrile, which is further dioxygenated to produce the observed cis-diol. A proposed mechanism for this transformation involves initial benzylic monooxygenation followed by a nitrene-mediated rearrangement to form an oxime, which is further dehydrated to afford the nitrile. To the best of our knowledge, this is the first report of enzymatic oxidation of an alkyl azide to a nitrile. In addition, the described oxime-dehydration activity has not been reported for Rieske dioxygenases.

Synthesis of (-)-6-hydroxyshikimic acid from ((5S,6R)-5,6-dihydroxy-1,3-cyclohexadienyl)methanenitrile

A six step synthesis of (-)-6-hydroxyshikimic acid 2 has been developed starting from ((5S,6R)-5,6-dihydroxy-1,3-cyclohexadienyl)methanenitrile 3, produced by biotransformation of cyanobenzene by the enzyme toluene dioxygenase.

Double [3,3]-sigmatropic rearrangement in the enzymatic dioxygenation of benzyl azide: Preparation of novel synthetically valuable azido-diols

Enzymatic dioxygenation of benzyl azide by toluene dioxygenase produces the expected enantiopure cis-cyclohexadienediol along with an exocyclic diene formed by a spontaneous sequence of two [3,3] sigmatropic shifts. This novel dienediol presents high synthetic potential for natural product synthesis. The sigmatropic rearrangements can be reversed by protection of the diol moiety. An optimized production protocol for either of these valuable diols is presented.

Aza and oxo Diels-Alder reactions using cis-cyclohexadienediols of microbial origin: Chemoenzymatic preparation of synthetically valuable heterocyclic scaffolds

Aza and oxo Diels-Alder reactions using enantiopure cis-cyclohexadienediols were studied. These dienediols were obtained from the biotransformation of monosubstituted arenes using bacterial dioxygenases (toluene and benzoate dioxygenases). Ethyl glyoxylate and its N-tosyl imine were used as dienophiles to afford the corresponding hetero Diels-Alder bicyclic adducts with excellent regio- and stereoselectivities. Quantum chemical calculations at the B3LYP/6-31+G(d,p) level of theory were performed to rationalize the observed selectivities especially the stereochemical aspects of the cycloadditions. The synthetic importance of these adducts is highlighted for the preparation of enantiopure 2,2,3,4,5,6-hexasubstituted piperidine and tetrahydropyran from toluene.

Enzymatic and chemoenzymatic synthesis and stereochemical assignment of cis-dihydrodiol derivatives of monosubstituted benzenes

Toluene dioxygenase-catalysed oxidation of mono-substituted benzene substrates (R = F, Cl, Br, I, Me, Et, CH2OAc, CH=CH2, C=CH, CF3, CN, OMe, OEt, SMe) in growing cultures of Pseudomonas putida UV4 yielded the corresponding cis-dihydrodiol metabolites. Palladium-catalysed cross-coupling of cis-(1S,2S)-1,2-dihydroxy-3-iodocyclohexa-3,5-diene with a range of tributyltin compounds provided a chemoenzymatic route to a further series of cis-dihydrodiol derivatives of monosubstituted benzenes (R = D, CH2CH=CH2, Bun, SEt, SPr1, SBu1, SPh, SC6H4Me-4). The enantiopurities and absolute configurations of the cis-dihydrodiols, obtained by both enzymatic and chemoenzymatic routes, were determined by several new methods including 1H NMR spectroscopic analysis of the bis-MTPA esters of the 4-phenyl-1,2,4-triazoline-3,5-dione cycloadducts, X-ray crystallography, circular dichroism spectroscopy and stereochemical correlation.

Syntheses of 6β-hydroxyshikimic acid and its derivatives

The conversion of (1S,2S)-3-bromocyclohexa-3,5-diene-1,2-diol, (5S,6S)-5,6-dihydroxycyclohexa-1,3-diene-1-carbonitrile and methyl (5S,6S)-5,6-dihydroxycyclohexa-1,3-diene-1-carboxylate into 6β-hydroxyshikimic acid and protected derivatives is described.

Enzymatic and Chemical Syntheses of cis-Dihydrodiol Derivatives of Monocyclic Arenes

Metabolism of bromobenzene and iodobenzene by growing cultures of Pseudomonas putida UV4 gave the corresponding cis-dihydrodiol products 1 and 2 in high yields; subsequent direct chemical substitution of the halogen atoms in these metabolites provided a new range of enantiomerically pure cis-dihydrodiols of known absolute configuration.