59919-09-4

Basic information

• Product Name: Cyclohexanone, 2-(phenylmethyl)-, (S)-
• CAS NO: 59919-09-4
• Molecular Formula: C13H16O
• Molecular Weight: 188.269
• Mol File: 59919-09-4.mol

Chemical Properties

• CAS DataBase Reference: Cyclohexanone, 2-(phenylmethyl)-, (S)-(CAS DataBase Reference)
• NIST Chemistry Reference: Cyclohexanone, 2-(phenylmethyl)-, (S)-(59919-09-4)
• EPA Substance Registry System: Cyclohexanone, 2-(phenylmethyl)-, (S)-(59919-09-4)

Safety Data

• Hazardous Substances Data: 59919-09-4(Hazardous Substances Data)

Upstream product

• 72170-99-1 [(S)-2-Benzyl-cyclohex-(Z)-ylidene]-((S)-2-methoxymethyl-pyrrolidin-1-yl)-amine 
• 6651-36-1 1-(Trimethylsilyloxy)cyclohexene 
• 108-94-1 cyclohexanone 
• 100-39-0 benzyl bromide 
• 86448-82-0 (+)-erythro-N-cyclohexylidene-2-methoxy-1,2-diphenylethylamine 
• 86448-82-0 (-)-erythro-N-cyclohexylidene-2-methoxy-1,2-diphenylethylamine 
• 67074-33-3 (S)-2-Cyclohexylideneamino-3-methyl-butyric acid tert-butyl ester 
• 81418-18-0 1-acetoxy-2-benzylcyclohexene 
• 130409-59-5 1-(propionyloxy)-2-benzylcyclohexene 
• 10468-40-3 cyclohexanone N-cyclohexylimine 
• 100-44-7 benzyl chloride 
• 139620-20-5 Isobutyric acid 2-benzyl-cyclohex-1-enyl ester 
• 139620-21-6 Benzoic acid 2-benzyl-cyclohex-1-enyl ester 
• 81523-07-1 2-benzyl-2-methoxycyclohexanone 

Downstream Products

• 161870-67-3 (2R,8S)-8-Benzyl-4-oxo-1,2,3,4,5,6,7,8-octahydro-quinoline-2-carboxylic acid 
• 123619-80-7 (1S,2S)-α-benzylcyclohexanol 
• 159690-58-1 (R)-7-benzyloxacycloheptan-2-one 

Relevant articles and documents

Indene Derived Phosphorus-Thioether Ligands for the Ir-Catalyzed Asymmetric Hydrogenation of Olefins with Diverse Substitution Patterns and Different Functional Groups

A family of phosphite/phosphinite-thioether ligands have been tested in the Ir-catalyzed asymmetric hydrogenation of a range of olefins (50 substrates in total). The presented ligands are synthesized in three steps from cheap indene and they are air-stable solids. Their modular architecture has been crucial to maximize the catalytic performance for each type of substrate. Improving most Ir-catalysts reported so far, this ligand family presents a broader substrate scope, covering different substitution patterns with different functional groups, ranging from unfunctionalized olefins, through olefins with poorly coordinative groups, to olefins with coordinative functional groups. α,β-Unsaturated acyclic and cyclic esters, ketones and amides werehydrogenated in enantioselectivities ranging from 83 to 99% ee. Enantioselectivities ranging from 91 to 98% ee were also achieved for challenging substrates such as unfunctionalized 1,1′-disubstituted olefins, functionalized tri- and 1,1′-disubstituted vinyl phosphonates, and β-cyclic enamides. The catalytic performance of the Ir-ligand assemblies was maintained when the environmentally benign 1,2-propylene carbonate was used as solvent. (Figure presented.).

Enantioselective decarboxylative protonation and deuteration of β-ketocarboxylic acids

Enantioselective decarboxylative protonation of tetralone-derived β-ketocarboxylic acids was achieved with up to 89% enantiomeric excess (ee)-in the presence of a chiral primary amine catalyst. Furthermore, this method was applied to enantioselective deuteration to afford the corresponding α-deuterioketones with up to 88% ee.

Highly Enantioselective Iridium-Catalyzed Hydrogenation of Conjugated Trisubstituted Enones

Asymmetric hydrogenation of conjugated enones is one of the most efficient and straightforward methods to prepare optically active ketones. In this study, chiral bidentate Ir-N,P complexes were utilized to access these scaffolds for ketones bearing the stereogenic center at both the α- and β-positions. Excellent enantiomeric excesses, of up to 99%, were obtained, accompanied with good to high isolated yields. Challenging dialkyl substituted substrates, which are difficult to hydrogenate with satisfactory chiral induction, were hydrogenated in a highly enantioselective fashion.

Rhodium-catalyzed asymmetric hydrogenation of exocyclic α,β-unsaturated carbonyl compounds

A highly enantioselective hydrogenation of exocyclic α,β-unsaturated carbonyl compounds catalyzed by Rh/bisphosphine-thiourea (ZhaoPhos) has been developed, giving the corresponding α-chiral cyclic lactones, lactams and ketones with high yields and excellent enantioselectivities (up to 99% yield and 99% ee). Remarkably, the hydrogen bond between the substrate and the catalyst plays a critical role in this transformation. The synthetic utility of this protocol has been demonstrated by efficient synthesis of chiral 3-(4-fluorobenzyl)piperidine, a key chiral fragment of bioactive molecules.

Enantioselective Protonation of Enol Esters with Bifunctional Phosphonium/Thiourea Catalysts

Bifunctional phosphonium/thioureas derived from tert-leucine behaved as highly selective catalysts for enantioselective protonation of enol esters, providing α-chiral ketones in yields of up to 99% with high enantioselectivities (up to 98.5:1.5 er). Control experiments clarified that a bulky tert-butyl group and phosphonium and thiourea moieties were necessary to achieve such high stereoselectivity. In addition, mechanistic investigations indicated the catalyst was converted to the corresponding betaine species, which served as a monomolecular catalyst.

Phosphite-thioether/selenoether Ligands from Carbohydrates: An Easily Accessible Ligand Library for the Asymmetric Hydrogenation of Functionalized and Unfunctionalized Olefins

A large family of phosphite-thioether/selenoether ligands has been easily prepared from accessible L-(+)-tartaric acid and D-(+)-mannitol and applied in the M-catalyzed (M=Ir, Rh) asymmetric hydrogenation of a broad number of substrates (46 in total). Its highly modular architecture has been crucial to maximize the catalytic performance. Improving most of the reported approaches, this ligand family presents a broad substrate scope. By selecting the ligand parameters high enantioselectivities (ee's up to 99 %) have therefore been achieved in a broad range of both, functionalized and unfunctionalized substrates. Interestingly, both enantiomers of the hydrogenation products can be usually achieved by changing the ligand parameters.

Giving a Second Chance to Ir/Sulfoximine-Based Catalysts for the Asymmetric Hydrogenation of Olefins Containing Poorly Coordinative Groups

This work identifies a family of Ir/phosphite-sulfoximine catalysts that has been successfully used in the asymmetric hydrogenation of olefins with poorly coordinative or noncoordinative groups. In comparison with analogue Ir/phosphine-sulfoximine catalysts previously reported, the presence of a phosphite group extended the range of olefins than can be efficiently hydrogenated. High enantioselectivities, comparable to the best ones reported, have been achieved for a wide range of olefins containing relevant poorly coordinative groups such as α,β-unsaturated enones, esters, lactones, and lactams as well as alkenylboronic esters.

Formation, Alkylation, and Hydrolysis of Chiral Nonracemic N-Amino Cyclic Carbamate Hydrazones: An Approach to the Enantioselective α-Alkylation of Ketones

The α-alkylation of ketones is a fundamental synthetic transformation. The development of asymmetric variants of this reaction is important given that numerous natural products, drugs, and related compounds exist as α-functionalized ketones or derivatives thereof. We previously reported our preliminary studies on the development of a new enantioselective ketone α-alkylation procedure using N-amino cyclic carbamate (ACC) auxiliaries. In comparison to other auxiliary-based methods, ACC alkylation offers a number of advantages and is both highly enantioselective and high yielding. Herein, we provide a full account of our studies on the enantioselective ACC ketone α-alkylation method.

Fluoride Anions in Self-Assembled Chiral Cage for the Enantioselective Protonation of Silyl Enol Ethers

The potential of Song's chiral oligoethylene glycols (oligoEGs) as catalysts was explored in the enantioselective protonation of trimethylsilyl enol ethers in combination with alkali metal fluoride (KF and CsF) and in the presence of a proton source. Highly enantioselective protonations of various silyl enol ethers of α-substituted tetralones were achieved, producing chiral α-substituted tetralones in full conversion and with up to 99% ee. The established protocol was successfully extended to the synthesis of biologically relevant chiral α-substituted chromanone and thiochromanone derivatives.

Alternatives to Phosphinooxazoline (t-BuPHOX) Ligands in the Metal-Catalyzed Hydrogenation of Minimally Functionalized Olefins and Cyclic β-Enamides

This study presents a new series of readily accessible iridium- and rhodium-phosphite/oxazoline catalytic systems that can efficiently hydrogenate, for the first time, both minimally functionalized olefins and functionalized olefins (62 examples in total) in high enantioselectivities (ees up to >99%) and conversions. The phosphite-oxazoline ligands, which are readily available in only two synthetic steps, are derived from previous privileged 4-alkyl-2-[2-(diphenylphosphino)phenyl]-2-oxazoline (PHOX) ligands by replacing the phosphine moiety by a biaryl phosphite group and/or the introduction of a methylene spacer between the oxazoline and the phenyl ring. The modular design of the ligands has given us the opportunity not only to overcome the limitations of the iridium-PHOX catalytic systems in the hydrogenation of minimally functionalized Z-olefins and 1,1-disubstituted olefins, but also to expand their use to unfunctionalized olefins containing other challenging scaffolds (e.g., exocyclic benzofused and triaryl-substituted olefins) and also to olefins with poorly coordinative groups (e.g., α,β-unsaturated lactams, lactones, alkenylboronic esters, etc.) with enantioselectivities typically >95% ee. Moreover, both enantiomers of the hydrogenation product could be obtained by simply changing the configuration of the biaryl phosphite moiety. Remarkably, the new catalytic systems also provided excellent enantioselectivities (up to 99% ee) in the asymmetric hydrogenation of another challenging class of olefins – the functionalized cyclic β-enamides. Again, both enantiomers of the reduced amides could be obtained by changing the metal from Ir to Rh. We also demonstrated that environmentally friendly propylene carbonate can be used with no loss of enantioselectivity. Another advantage of the new ligands over the PHOX ligands is that the best ligands are derived from the affordable (S)-phenylglycinol rather than from the expensive (S)-tert-leucinol. (Figure presented.).