113301-48-7

Basic information

• Product Name: S-(+)-2-Octanol
• Synonyms: 2-Octanol, (2S)-; 2-Octanol, (S)-; d-Octan-2-ol; D(+)-2-Octanol; (S)-octan-2-ol; (S)-2-Octanol
• CAS NO: 113301-48-7
• Molecular Formula: C₈H₁₈O
• Molecular Weight: 130.23
• EINECS: 228-213-6
• Mol File: 113301-48-7.mol
• Article Data: 581

Chemical Properties

• Boiling Point: 175℃
• Flash Point: 71℃
• Density: 0.822
• Refractive Index: 1.425-1.427
• Water Solubility: 1 g/L (20℃)
• CAS DataBase Reference: S-(+)-2-Octanol(CAS DataBase Reference)
• NIST Chemistry Reference: S-(+)-2-Octanol(113301-48-7)
• EPA Substance Registry System: S-(+)-2-Octanol(113301-48-7)

Safety Data

• Hazard Codes: Xi:Irritant
• Statements: R36/37/38:
• Safety Statements: S26:; S36:
• Hazardous Substances Data: 113301-48-7(Hazardous Substances Data)

Upstream product

• 917-64-6 methyl magnesium iodide 
• 111-71-7 heptanal 
• 111-86-4 n-Octylamine 
• 64-17-5 ethanol 
• 74-85-1 ethene 
• 7214-62-2 2-octyl nitrite 
• 1577-55-5 octadec-9-ene-1,12-diol 
• 111-66-0 oct-1-ene 
• 101-97-3 Ethyl 2-phenylethanoate 
• 111-13-7 hexyl-methyl-ketone 
• 3234-26-2 2,3-epoxyoctane 
• 110-43-0 n-pentyl methyl ketone 
• 917-54-4 methyllithium 
• 2747-38-8 methyltrichlorotitanium 

Downstream Products

• 109845-03-6 bis-((R)-1-methyl-heptyloxy)-phenyl-borane 
• 59078-33-0 octan-2-yl 3-phenylpropiolate 
• 7598-65-4 (+)(S:S:S)-tris-(1-methyl-heptyl)-phosphite 
• 18023-52-4 trimethyl-(1-methyl-heptyloxy)-silane 
• 102462-53-3 diphenyl-dithiophosphinic acid-(1-methyl-heptyl ester) 
• 124591-00-0 N,N'-bis-(4-dimethylamino-phenyl)-terephthalamide 
• 24848-81-5 B(O-2-C₈H₁₇)3 
• 111-13-7 hexyl-methyl-ketone 
• 100879-95-6 (S)-chloro-(1-methyl-heptyloxy)-phenyl-borane 
• 109845-03-6 bis-((S)-1-methyl-heptyloxy)-phenyl-borane 
• 112867-61-5 ((S)-1-methyl-heptyloxy)-diphenyl-borane 
• 24848-81-5 (+)-tris{octyl⁽²⁾oxy}}borane 
• 5978-55-2 (2R)-2-bromooctane 
• 100879-95-6 (R)-chloro-(1-methyl-heptyloxy)-phenyl-borane 

Relevant articles and documents

Enantioselectivity and catalysis improvements of Pseudomonas cepacia lipase with Tyr and Asp modification

A concise strategy to improve the p-NPP (p-nitrophenyl palmitate) catalytic activity and enantioselectivity towards secondary alcohols of Pseudomonas cepacia lipase (PcL) has been described. The PcL was modified by I3-, N-acetyl imidazole (NAI), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC) and ethylenediamine (EDA) in the absence or presence of n-hexane, respectively. After being modified by the four modification reagents, the enantioselectivity (E value) of the PcL towards secondary alcohols was enhanced by 2- to 4-fold. The catalytic activity of EDA-PcL was increased by about 6-fold. The matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis of modified PcL showed that Tyr4, Tyr29, Tyr45, Tyr95, Asp36 and Asp55 were the modified sites. When Tyr29 was modified, the E value of PcL towards secondary alcohols was largely improved. MALDI-TOF-MS characterization and molecular dynamics simulation of the lipase indicated that Tyr29 located inside the catalytic cavity had a significant impact on the E value. The strong steric hindrance of acetyl and iodine ion to the groups on the chiral center of the substrates is responsible for the improvement. In addition, the enhancement of hydrophobicity on the surface of the lipase due to the sidechain replacement of Asp with uncharged hydrophobic groups also improved the E value.

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Screening of a minimal enriched P450 BM3 mutant library for hydroxylation of cyclic and acyclic alkanes

A minimal enriched P450 BM3 library was screened for the ability to oxidize inert cyclic and acyclic alkanes. The F87A/A328V mutant was found to effectively hydroxylate cyclooctane, cyclodecane and cyclododecane. F87V/A328F with high activity towards cyclooctane hydroxylated acyclic n-octane to 2-(R)-octanol (46% ee) with high regioselectivity (92%).

The Enantioface-Differentiating Hydrogenation of the C=O Double Bond with Asymmetrically Modified Raney Nickel. XXXIX. Repeated Uses of the Catalyst in the Hydrogenation of 2-Alkanones

The durability of tartaric acid-sodium bromide-modified Raney nickel in the hydrogenation of 2-octanone was investigated.A remarkable lowering of the optical yield was observed in the repeated use of the catalyst.A lack of sodium ions in the reaction system was found to be the origin of this phenomenon.The addition of sodium ions to the reaction mixture was useful for attaining high optical yields in the repeated uses of the catalyst.

Acceleration of the Hydrogenation of 2-Octanone with an Alkali Salt of an Organic Acid

The hydrogenation of 2-octaone over various types of nickel catalysts was found to be accelerated by the addition of small amounts of carboxylates of alkali metals such as Na, K, and Li.

Baker's yeast-induced asymmetric reduction of α-ketosulfides: Synthesis of optically active 1-(benzothiazol-2-ylsulfanyl)-2- alkanols, 2-alkanols, and thiiranes

1-(Benzothiazol-2-ylsulfanyl)-2-alkanols 3 were prepared in very high enantiomeric excess by baker's yeast-induced asymmetric reduction of 1- (benzothiazol-2-ylsulfanyl)-2-alkanones 1. Conversion of 3 into optically active simple 2-alkanols 4 and thiiranes 2 by reductive desulfurization and base treatment, respectively, is also described. The absolute configuration of the new compounds synthesized has been established by chemical correlation and specific rotation comparison.

Chemoenzymatic Deracemization of Secondary Alcohols by using a TEMPO-Iodine-Alcohol Dehydrogenase System

A deracemization system for secondary alcohols was established after the analysis of individual steps and their compatibility in one pot. The chemical oxidation and bioreduction occurred in a sequential manner to yield 1-arylethanols and lineal aliphatic alcohols with excellent conversions and enantiomeric excess values. The oxidation step was performed by using 2,2,6,6-tetramethylpiperidin-1-oxyl and iodine. This chemical process was extremely favored by sonication, which allowed quantitative formation of the corresponding ketone intermediates after just 1 h. Simple destruction of iodine in the same pot allowed sequential bioreduction of the ketones by using either Prelog or antiPrelog enzymes, which led to the preparation of the enantiopure alcohols in excellent yields. Just a sec: The one-pot deracemization of secondary alcohols involving oxidation with 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and iodine followed by alcohol dehydrogenase (ADH)-catalyzed bioreduction is described. 1-Arylethanols and lineal aliphatic alcohols are obtained with excellent conversions and enantiomeric excess values. LBADH=alcohol dehydrogenase from Lactobacillus brevis.

UEBER DIE ALDEHYDSELEKTIVITAET VON ALKYLKOMPLEXEN VON SCANDIUM, YTTRIUM, LANTHAN UND LANTHANIDEN IN ALDEHYD/KETON-KONKURRENZVERSUCHEN

In-situ prepared alkyl complexes Hal2M-Alk (Alk = Me, Bu) of the f-metals Ce, Pr, Nd, Sm, Gd exhibit very low selectivity in competition experiments between heptanal and diethylketone in THF, whereas the selectivity of complexes Hal2M-Me (M = Sc, Y, La) is distinctly higher with decreasing tendency in the sequence Sc>Y>La.These and previously reported results led to a general working hypothesis about the reasons of the aldehyde-selectivity of transition metal alkyls.

ASYMMETRIC TRANSFER HYDROGENATION OF KETONES CATALYZED BY PHOSPHINE-RHODIUM(I) AMD -IRIDIUM(I) COMPLEXES

The asymmetric hydrogen transfer from propan-2-ol to prochiral ketones is effectively catalyzed by diphosphine complexes of iridium and rhodium.The influence of the reaction conditions on the activity and selectivity of the catalysts has been investigated.

Application of robust ketoreductase from Hansenula polymorpha for the reduction of carbonyl compounds

Enzyme-catalysed asymmetric reduction of ketones is an attractive tool for the production of chiral building blocks or precursors for the synthesis of bioactive compounds. Expression of robust ketoreductase (KRED) from Hansenula polymorpha was upscaled and applied for the asymmetric reduction of 31 prochiral carbonyl compounds (aliphatic and aromatic ketones, diketones and β-keto esters) to the corresponding optically pure hydroxy compounds. Biotransformations were performed with the purified recombinant KRED together with NADP+ recycling glucose dehydrogenase (GDH, Bacillus megaterium), both overexpressed in Escherichia coli BL21(DE3). Maximum activity of KRED for biotransformation of ethyl-2-methylacetoacetate achieved by the high cell density cultivation was 2499.7 ± 234 U g–1DCW and 8.47 ± 0.40 U·mg–1E, respectively. The KRED from Hansenula polymorpha is a very versatile enzyme with broad substrate specificity and high activity towards carbonyl substrates with various structural features. Among the 36 carbonyl substrates screened in this study, the KRED showed activity with 31, with high enantioselectivity in most cases. With several ketones, the Hansenula polymorpha KRED catalysed preferentially the formation of the (R)-secondary alcohols, which is highly valued.

Enzymatic resolution of alcohols via lipases immobilized in microemulsion-based gels

Lipases immobilized in microemulsion-based gel (MBG) were used in the resolution of racemic alcohols, in a new, convenient method of catalysis in organic solvents which employs small amounts of the enzyme.

Glycerol as solvent and hydrogen donor in transfer hydrogenation-dehydrogenation reactions

Glycerol is employed successfully as a green solvent and hydrogen donor in catalytic transfer hydrogenation-dehydrogenation reactions. The glycerol donates hydrogen to various unsaturated organic compounds under mild reaction conditions and as a solvent, allows easy separation of products and catalyst recycling.

Acid-catalyzed rearrangement of α-hydroxytrialkylsilanes

Cationic rearrangement of several α-hydroxysilanes is described. Treatment of both (1R,1′R,2′S)-α-hydroxycyclopropylsilane syn-9 and (1S,1′R,2′S)-anti-9 under aqueous H2SO4 underwent rearrangement via a common α-silyl cation intermediate A to give a mixture of the ring-opened (R)-vinylsilane 13, the tandem [1,2]-CC bond migration product (1R,2S,1′R)-14, and its 1′S isomer 15. On the other hand, the acidic treatment of (R,E)-α-hydroxyalkenylsilane 8 or (R,Z)-8 was each accompanied with partial racemization to give an enantiomeric isomer of allylic alcohol 23 via a preferential syn-facial SN2′ reaction, respectively. Both α-hydroxyalkynylsilane 6 and α-hydroxyalkylsilane 12 were inert to the acidic conditions; however, treatment of (R)-α-mesyloxyalkynylsilane 26 under aqueous H2SO4 gave a mixture of the optically active rearranged allene 27, α,β-unsaturated ketone 28, and (S)-α-hydroxyalkynylsilane 6 with partial racemization. Comparisons of the reactivities of these α-hydroxysilanes under acidic conditions are also disclosed.

ASYMMETRIC REDUCTION OF PROCHIRAL KETONES WITH A CHIRAL REDUCING AGENT PREPARED FROM STANNOUS CHLORIDE, CHIRAL DIAMINE AS A LIGAND, AND DIISOBUTYLALUMINUM HYDRIDE

A new chiral reducing agent, prepared by treatment of a mixture of stannous chloride and a chiral diamine derived from (S)-proline with diisobutylaluminum hydride, is effective for asymmetric reduction of prochiral ketones.

Highly enantioselective biohydrolysis of sec-alkyl sulfate esters with inversion of configuration catalysed by Pseudomonas spp.

In search of highly enantioselective microbial sec-alkyl sulfatase activity, a broad screening among bacteria, fungi and Archaea revealed several Ralstonia and Pseudomonas spp. as valuable sources, whereas fungi were completely inactive. In particular, Pseudomonas sp. DSM 6611 was able to hydrolyse the (R) enantiomers of a broad range of rac-sec-alkyl sulfate esters with excellent enantioselectivities (E > 200) to furnish the corresponding inverted (S)-sec-alcohols in high ee's. The substrate range of this organism was remarkably broad and bulky groups were also nicely tolerated. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Maximise equilibrium conversion in biphasic catalysed reactions: How to obtain reliable data for equilibrium constants?

For the prediction and optimisation of the equilibrium conversion in biphasic catalysed reactions, the equilibrium constant of the desired reaction and the partition coefficients of all reactants have to be known. Within this contribution we have examined the alcohol dehydrogenase-catalysed reduction of several linear and aromatic ketones in biphasic reaction media with respect to equilibrium conversion. In this example, the equilibrium constant can be expressed in terms of differences in oxidation-reduction potentials ΔE0. However, for a large variety of organic compounds, these data are quite rare in the literature. To overcome this lack of data, we have utilised methods of computational chemistry to calculate data for the Gibbs free energy ΔGR leading to the equilibrium constants of a homologous series of linear ketones. To obtain comparable data for the reduction of substituted acetophenone derivatives, the Hammett relation leads to the necessary equilibrium constants. Furthermore, we compare the equilibrium conversions of a set of cofactor regeneration methods for the alcohol dehydrogenase-catalysed reductions. These results lead to a time-saving experimental design for the enantioselective reduction of 2-octanone to (R)-2-octanol on a preparative scale utilising biphasic reaction conditions.

Organoboron Compounds in Organic Synthesis. 2. Asymmetric Reduction of Dialkyl Ketones with (R,R)- or (S,S)-2,5-Dimethylborolane

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Base free: N -alkylation of anilines with ArCH2OH and transfer hydrogenation of aldehydes/ketones catalyzed by the complexes of η5-Cp?Ir(III) with chalcogenated Schiff bases of anthracene-9-carbaldehyde

The condensation of anthracene-9-carbaldehyde with 2-(phenylthio/seleno)ethylamine results in Schiff bases [PhS(CH2)2CN-9-C14H9](L1) and [PhSe(CH2)2CN-9-C14H9] (L2). On their reaction with [(η5-Cp?)IrCl(μ-Cl)]2 and CH3COONa at 50 °C followed by treatment with NH4PF6, iridacycles, [(η5-Cp?)Ir(L-H)][PF6] (1: L = L1; 2: L = L2), result. The same reaction in the absence of CH3COONa gives complexes [(η5-Cp?)Ir(L)Cl][PF6] (3-4) in which L = L1(3)/L2(4) ligates in a bidentate mode. The ligands and complexes were authenticated with HR-MS and NMR spectra [1H, 13C{1H} and 77Se{1H} (in the case of L2 and its complexes only)]. Single crystal structures of L2 and half sandwich complexes 1-4 were established with X-ray crystallography. Three coordination sites of Ir in each complex are covered with η5-Cp? and on the remaining three, donor atoms present are: N, S/Se and C-/Cl-, resulting in a piano-stool structure. The moisture and air insensitive 1-4 act as efficient catalysts under mild conditions for base free N-alkylation of amines with benzyl alcohols and transfer hydrogenation (TH) of aldehydes/ketones. The optimum loading of 1-4 as a catalyst is 0.1-0.5 mol% for both the activations. The best reaction temperature is 80 °C for transfer hydrogenation and 100 °C for N-alkylation. The mercury poisoning test supports a homogeneous pathway for both the reactions catalyzed by 1-4. The two catalytic processes are most efficient with 3 followed by 4 > 1 > 2. The mechanism proposed on the basis of HR-MS of the reaction mixtures of the two catalytic processes taken after 1-2 h involves the formation of an alkoxy and hydrido species. The real catalytic species proposed in the case of iridacycles results due to the loss of the Cp? ring.

Highly enantioselective sec-alkyl sulfatase activity of the marine planctomycete Rhodopirellula baltica shows retention of configuration

(Chemical Equation Presented) Hydrolytic enzymes: The marine planctomycete Rhodopirellula baltica DSM 10527 displays high stereo- and enantioselective alkyl sulfatase activity towards (±)-sec-alkyl sulfates with retention of configuration through cleavage of their S-O bond (see scheme; pathway B), whereas inversion of configuration is observed upon cleavage of the C-O bond (pathway A).

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Structural basis for a highly (S)-enantioselective reductase towards aliphatic ketones with only one carbon difference between side chain

Aliphatic ketones, such as 2-butanone and 3-hexanone, with only one carbon difference among side chains adjacent to the carbonyl carbon are difficult to be reduced enantioselectively. In this study, we utilized an acetophenone reductase from Geotrichum candidum NBRC 4597 (GcAPRD) to reduce challenging aliphatic ketones such as 2-butanone (methyl ethyl ketone) and 3-hexanone (ethyl propyl ketone) to their corresponding (S)-alcohols with 94% ee and > 99% ee, respectively. Through crystallographic structure determination, it was suggested that residue Trp288 limit the size of the small binding pocket. Docking simulations imply that Trp288 plays an important role to form a C-H?π interaction for proper orientation of ketones in the pro-S binding pose in order to produce (S)-alcohols. The excellent (S)-enantioselectivity is due to a non-productive pro-R binding pose, consistent with the observation that the (R)-alcohol acts as an inhibitor of (S)-alcohol oxidation.

Enantioselective stereoinversion of sec-alkyl sulfates by an alkylsulfatase from Rhodococcus ruber DSM 44541

Enantioselective biohydrolysis of sec-alkyl sulfate esters using a bacterial alkylsulfatase from Rhodococcus ruber DSM 44541 proceeded in a stereoselective fashion though inversion of configuration. Thus, from racemic substrates, the corresponding (R)-enantiomers were hydrolyzed selectively to furnish the corresponding sec-alcohol and non-reacted sulfate ester, both of (S)-configuration, which represents a homochiral product mixture. The enantioselectivities were found to depend on the substrate structure and were optimal for sec-sulfate esters in the ω-1 position (up to E=21). Since the enzyme was inactive on prim-sulfate esters, it can be classified as a sec-alkylsulfatase [EC 3.1.6.X].

Recycling of the ionic liquid phase in process integrated biphasic whole-cell biocatalysis

Ionic liquids (IL) show a large set of interesting physicochemical properties, which make them an interesting alternative to commonly used organic solvents for applications in biphasic whole-cell biocatalysis. However, the currently still large cost of this class of solvents makes their use in industrial processes only competitive if the ionic liquid phase is recycled without loss of productivity during the process. Exemplarily for such an application, the asymmetric reduction of 2-octanone to (R)-2-octanol by a recombinant Escherichia coli overexpressing the Lactobacillus brevis alcohol dehydrogenase (ADH) and the Candida boidinii formate dehydrogenase (FDH) in biphasic ionic liquid/water systems was considered in this work. The repeated use of the ionic liquid phase was studied in a reaction system containing 20% (v/v) 1-hexyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([HMPL][NTF]) and a substrate concentration of 300 mM 2-octanone in the ionic liquid phase. 25 batch biotransformations were performed followed by phase separation, product isolation through distillation and reuse of the ionic liquid. No decrease in conversion was experienced during the 25 subsequent batch biotransformations. The average conversion was 98.5 (±0.7)%, and enantiomeric excesses were constant at values ≥99.5% (R). Over all cycles, a total of 999 (±6) g (R)-2-octanol LIL-1 was produced.

A Method for the Synthesis of Enantiomerically Pure Alkanols by Reductive Desulfurization of Thiophene-Alcohols

Acetals 3 and 4 of alkylthienylcarbinols 1 were prepared using an enantiomerically pure lactol 2.In the key step these compounds were desulfurized.After deprotection the target compounds 7 and ent-7 were obtained.Keywords.Acetals; Desulfurization; Enantiomerically pure alkanoles; Thiophenemethanol derivatives.

Regiodivergent Reductive Opening of Epoxides by Catalytic Hydrogenation Promoted by a (Cyclopentadienone)iron Complex

The reductive opening of epoxides represents an attractive method for the synthesis of alcohols, but its potential application is limited by the use of stoichiometric amounts of metal hydride reducing agents (e.g., LiAlH4). For this reason, the corresponding homogeneous catalytic version with H2 is receiving increasing attention. However, investigation of this alternative has just begun, and several issues are still present, such as the use of noble metals/expensive ligands, high catalytic loading, and poor regioselectivity. Herein, we describe the use of a cheap and easy-To-handle (cyclopentadienone)iron complex (1a), previously developed by some of us, as a precatalyst for the reductive opening of epoxides with H2. While aryl epoxides smoothly reacted to afford linear alcohols, aliphatic epoxides turned out to be particularly challenging, requiring the presence of a Lewis acid cocatalyst. Remarkably, we found that it is possible to steer the regioselectivity with a careful choice of Lewis acid. A series of deuterium labeling and computational studies were run to investigate the reaction mechanism, which seems to involve more than a single pathway.

Biocatalytic synthesis of non-vicinal aliphatic diols

Biocatalysts are receiving increased attention in the field of selective oxyfunctionalization of C-H bonds, with cytochrome P450 monooxygenases (CYP450s), and the related peroxygenases, leading the field. Here we report on the substrate promiscuity of CYP505A30, previously characterized as a fatty acid hydroxylase. In addition to its regioselective oxyfunctionalization of saturated fatty acids (ω-1-ω-3 hydroxylation), primary fatty alcohols are also accepted with similar regioselectivities. Moreover, alkanes such as n-octane and n-decane are also readily accepted, allowing for the production of non-vicinal diols through sequential oxygenation. This journal is

Supported ionic liquid-like phases as efficient solid ionic solvents for the immobilisation of alcohol dehydrogenases towards the development of stereoselective bioreductions

Polymeric materials containing ionic liquid fragments, like those found in bulk ILs, are excellent solid media for the immobilisation of biocatalysts. Herein, the entrapment of the enzymatic system formed by alcohol dehydrogenase from Rhodococcus ruber (ADH-A) overexpressed in E. coli and its coenzyme has been studied. The activity, stability and reusability of these preparations have been investigated in the bioreduction of prochiral ketones finding excellent levels of conversion and selectivity. Interestingly, the immobilised enzyme remained active and exhibited excellent stability in aqueous solutions after several recycling uses. More importantly, these biopolymer materials retained most of their activity after consecutive reaction cycles, prolonged storage and under flow conditions.