113829-97-3

Basic information

• Product Name: (R)-3-phenylcyclohexanone
• CAS NO: 113829-97-3
• Molecular Weight: 174.243
• Mol File: 113829-97-3.mol
• Article Data: 196

Chemical Properties

• CAS DataBase Reference: (R)-3-phenylcyclohexanone(CAS DataBase Reference)
• NIST Chemistry Reference: (R)-3-phenylcyclohexanone(113829-97-3)
• EPA Substance Registry System: (R)-3-phenylcyclohexanone(113829-97-3)

Safety Data

• Hazardous Substances Data: 113829-97-3(Hazardous Substances Data)

Upstream product

• 930-68-7 cyclohexenone 
• 1728-18-3 dimethylacetal of cyclohexenone 
• 100-58-3 phenylmagnesium bromide 
• 115880-50-7 (R)-2-phenoxypropanoic acid methyl ester 
• 396718-95-9 [(R)-3-Phenyl-cyclohex-(E)-ylidene]-acetaldehyde 
• 98-80-6 phenylboronic acid 
• 28557-00-8 phenylzinc chloride 
• 108-86-1 bromobenzene 
• 10345-87-6 3-phenylcyclohex-2-enone 
• 100-59-4 phenylmagnesium chloride 
• 1765-93-1 4-fluoroboronic acid 
• 504-02-9 1,3-cylohexanedione 
• 591-50-4 iodobenzene 
• 23665-09-0 phenylzinc iodide 

Downstream Products

• 76936-85-1 (+)-(R)-3-phenyl-1-(2-tolyl)cyclohexene 
• 1232059-79-8 C₁₃H₁₉N 
• 1232059-70-9 (1S,3R)-3-phenyl-cyclohexanecarboxylic acid amide 
• 1232059-56-1 C₁₃H₁₅N 
• 1232059-68-5 (1R,3R)-3-phenyl-cyclohexanecarboxylic acid amide 
• 1232059-66-3 C₁₃H₁₆O₂ 

Relevant articles and documents

First examples of improved catalytic asymmetric C-C bond formation using the monodentate ligand combination approach

(Matrix presented) Using a combination of chiral monodentate phosphoramidite ligands in the rhodium-catalyzed conjugate addition of boronic acids to three different substrates, we have shown for the first time that the ligand combination approach is applicable for C-C bond formation. Chiral catalysts based on hetero-combinations of ligands are found to be more effective than the homo-combinations, 31P NMR experiments show that the hetero-combinations are formed in excess over the homo-combinations.

Synthesis, Characterization, and Application of Segphos Derivative Having Diferrocenylphosphino-Donor Moieties

An axially chiral bisphosphine, Fc-Segphos (1), which possesses diferrocenylphosphino-donor moieties, was prepared as a racemate, and its optical resolution was achieved by the use of chiral HPLC. Ligand 1 coordinated to a palladium(II) cation in a bidentate fashion to construct a unique chiral environment at the palladium center due to the sterically demanding ferrocenyl groups. Ligand (R)-1 was applied in the palladium-catalyzed asymmetric synthesis of axially chiral allenes showing good enantioselectivity of up to 92% ee. In general, (R)-1 displayed better enantioselectivity than the parent Segphos in the palladium-catalyzed reaction, and the Pd/(R)-1 species showed up to 18% ee enhancement over the (R)-Segphos-derived palladium catalyst.

Steric Tuning of Sulfinamide/Sulfoxides as Chiral Ligands with C1, Pseudo-meso, and Pseudo-C2 Symmetries: Application in Rhodium(I)-Mediated Arylation

A new family of sulfinamide/sulfoxide derivatives was synthesized as chiral bidentate ligands by stereoselective additions of methylsulfinyl carbanions to N-tert-butylsulfinylimines. The new ligands, with C1, pseudo-meso, and pseudo-C2 symmetries, were successfully assayed in Rh-catalyzed additions of arylboronic acids to activated ketones. The sterically dissymmetric C1 ligand (RS,SC,RS)-N-[1-(phenylsulfinyl)-3-methylbut-2-yl] tert-butylsulfinamide turned out to be the optimal one, allowing the 1,4-additions of diverse arylboronic acids, on different α,β-unsaturated cyclic ketones with high chemical yields and enantioselectivities up to >99% ee.

Enantioselective palladium-catalysed conjugate addition of arylsiloxanes

The complex formed from Pd(CH3CN)4(BF 4)2 and (R,R)-MeDUPHOS is a highly enantioselective catalyst for the asymmetric conjugate addition of aryltriethylsiloxanes to a variety of unsaturated ketones, lactones and

Synthesis of novel chiral phosphine-olefin complexes and their evaluation as ligands in the rhodium-catalyzed asymmetric 1,4-addition

Novel chiral phosphine-olefin complexes containing ferrocene and cyrhetrene backbones have been synthesized and evaluated as ligands in the rhodium-catalyzed 1,4-addition of phenylboronic acid to cyclohexenone. The highest efficiency in this series was ob

Rhodium-catalyzed asymmetric 1,4-additions, in water at room temperature, with in-flask catalyst recycling

Using the newly introduced designer surfactant polyethylene glycol ubiquinol sebacate (PQS), as the platform for micellar catalysis, non-racemic BINAP has been covalently attached and rhodium(I) inserted to form PQS-BINAP-Rh. This species, the first examp

Chiral thiophosphoramide and thioamide ligands in catalytic asymmetric carbon-carbon bond-formation reactions

Metal complexes with organosulfur ligands exist widely in nature. The high polarizability of the electrons on the sulfur atoms is responsible for a variety of structures and the reactivity of metal complexes with sulfur-containing ligands. Organosulfur-containing chiral ligands have various applications in catalytic asymmetric reactions. Our group has been interested in the applications of a series of thiophosphoramide and thioamide ligands in asymmetric carbon-carbon bond-formation reactions. In this account, we describe the synthesis of chiral thiophosphoramide and thioamide ligands and their applications in catalytic asymmetric carbon-carbon bond formation. Georg Thieme Verlag Stuttgart.

Palladium-catalyzed asymmetric 1,6-addition of diarylphosphines to α,β,γ,δ-unsaturated sulfonic esters: Controlling regioselectivity by rational selection of electron-withdrawing groups

Palladium-catalyzed asymmetric 1,6-addition of diarylphosphines to electron-deficient dienes was developed through rational selection of electron-withdrawing groups on the dienes. Various chiral allylic phosphine derivatives were synthesized in good yield

Highly enantioselective Cu-catalysed asymmetric 1,4-addition of diphenylzinc to cyclohexenone

Highly enantioselective Cu-catalysed 1,4-addition of diphenylzinc to cyclohexenone has been achieved for the first time using a monodentate phosphoramidite ligand.

Flexible C2-symmetric bis-sulfoxides as ligands in enantioselective 1,4-addition of boronic acids to electron-deficient alkenes

The application of acyclic C2-symmetric chelating bis-sulfoxide ligands in the Rh(I)-catalyzed enantioselective 1,4-addition of boronic acids to electron-deficient alkenes is reported. Among the acyclic ethane-bridged bis-sulfoxides tested, the

Base-Free Conditions for Rhodium-Catalyzed Asymmetric Arylation to Produce Stereochemically Labile α-Aryl Ketones

The asymmetric arylation of 2,2-dialkyl cyclopent-4-ene-1,3-diones with aryl boronic acids was found to be efficiently catalyzed by a chiral diene-rhodium μ-chloro dimer, [{RhCl((R)-diene?)}2], in the absence of bases in toluene/H2O to give 2,2-dialkyl 4-aryl cyclopentane-1,3-diones in high yields with high enantioselectivity. Such compounds can not be obtained with high enantiomeric purity under the standard basic conditions used for rhodium-catalyzed asymmetric arylation because the α-aryl ketone products undergo racemization under the basic conditions. Forget about bases, score a home run: The asymmetric arylation of 2,2-dialkyl cyclopent-4-ene-1,3-diones with aryl boronic acids was efficiently catalyzed by a chiral diene-rhodium μ-chloro dimer without a base in toluene/H2O (see scheme). The resulting α-aryl ketones can not be obtained with high ee values under the standard basic conditions for rhodium-catalyzed asymmetric arylation owing to their racemization in the presence of a base.

Asymmetric Addition of Aryl Boron Reagents to Enones with Rhodium Dicyclophane Imidazolium Carbene Catalysis

Chiral N-heterocyclic carbene ligands based on [2.2]paracyclophanes form complexes with rhodium. These catalysts can be used in the high-yielding and enantioselective asymmetric conjugate addition of arylboron compounds to cyclic and acyclic enones (see scheme).

Electron-poor chiral diphosphine ligands: High performance for rh-catalyzed asymmetric 1,4-addition of arylboronic acids at room temperature

Electron-poor chiral diphosphine ligands, MeO-F28-BIPHEP (1a) and MeO-F12-BIPHEP (1b), were synthesized for controlling a transition-metal catalyst electronically. The 1b-ligated Rh catalyst showed excellent catalytic activity with high % ee for asymmetri

Asymmetric dearomatization of η2-arene complexes: Synthesis of stereodefined functionalized cyclohexenones and cyclohexenes

A nonracemic η2-arene complex (2) was prepared from (R)-(+)-methyl-2- phenoxypropionate and pentaammineosmium(II) with high coordination diastereoselectivity (>9:1). Complex 2 was then treated with HOTf, an acetal, or a Michael acceptor to gene

Enantioselective conjugate addition of phenylboronic acid to enones catalysed by a chiral tropos/atropos rhodium complex at the coalescence temperature

A highly enantioselective rhodium-catalysed conjugate addition of phenylboronic acid to cyclic enones has been achieved using a dynamic library of chiral phosphorus ligands; the tropos/atropos nature of the ligands in the rhodium complex has been characterised via 31P-NMR. The Royal Society of Chemistry 2005.

Conjugate Additions of Organocuprates to Cycloalkenone Complexes of the Chiral Rhenium Lewis Acid 5-C5H5)Re(NO)(PPh3)>(+). Enantioselective Syntheses of 3-Substituted Cycloalkanones

Reactions of organocuprates R2CuLi and cycloalkenone complexes (+)-(R)-(+)BF4(-) (n = 2, 1) are conducted in THF or CH2Cl2 between -15 deg C and -116 deg C.Workups with aqueous HI give the corresponding 3-substituted cycloalkanones and iodide complex (η5-C5H5)Re(NO)(PPh3) (I).Under optimized conditions, 3-substituted cyclohexanones are obtained in 39-83percent yields and 64-86percent ee (R = Me, R; n-Bu, R; t-Bu, S; Ph, S or R), and 3-substituted cyclopentanones are obtained in 50-73percent yields and 79-93percent ee (R = Me, R; Ph, S).Evidence for intermediate enolate complexes is presented, protocols for recycling the chiral rhenium auxiliary are described, and possible mechanisms of 1,4-asymmetric induction are discussed.

Reducing Diastereomorphous Bis(phosphane oxide) Atropisomers to One Atropisomerically Pure Diphosphane: A New Ligand and a Novel Ligand-Preparation Design

1,1′-Biphenyl-2,2′-diphosphanes with an achiral bridge spanning C-5 and C-5′ form atropisomers that are enantiomers. Accessing them in an atropisomerically pure form requires resolving a racemic mixture thereof or of a bis(phosphane oxide) precursor. 1,1′-Biphenyl-2,2′-diphosphanes with a homochiral bridge spanning C-5 and C-5′ form atropisomers that are diastereomers. We synthesized the first compound of this kind 1) atropselectively and 2) under thermodynamic control—seemingly a first-time exploit in diphosphane synthesis. The selectivity-inducing step was a high-temperature reduction of two non-interconverting bis(phosphane oxide) atropisomers (60:40 mixture). It furnished the desired diphosphane atropisomerically pure (and atropconvergently because the yield was 67 %). This diphosphane proved worthwhile in Tsuji–Trost allylations, the Hayashi addition of phenylboronic acid to cyclohexenone, and the asymmetric hydrogenation of methyl acetoacetate (up to 95 % yield and 95 % ee).

Multicomponent synthesis of chiral bidentate unsymmetrical unsaturated N-heterocyclic carbenes: Copper-catalyzed asymmetric C-C bond formation

A multicomponent strategy was applied to the synthesis of chiral bidentate unsaturated hydroxyalkyl- and carboxyalkyl-N-heterocyclic carbene (NHC) precursors. The newly developed low-cost chiral ligands derived from amino alcohols and amino acids were eva

trans-Cyclooctenes as Chiral Ligands in Rhodium-Catalyzed Asymmetric 1,4-Additions

trans-Cyclooctenes serve as asymmetric ligands for the rhodium-catalyzed 1,4-additions of organotin reagents to enones. We demonstrate, for the first time, that these chiral olefins can provide efficient coordination spheres for asymmetric metal catalysis. As the asymmetric environment around the reaction site is constructed by the trans-cyclooctene framework, the introduction of a substituent at the allylic position further improves enantioselectivity to 93 % ee. These findings provide new chiral framework designs for the asymmetric ligands of metal catalysts.

Planar-chiral cyrhetrenes for the rhodium-catalyzed asymmetric 1,4-addition and the hydrogenation of enamides

The syntheses of novel cyrhetrenes 7a-c and 8a,b are described. These planar-chiral, mono- and diphosphines have been applied as ligands in the Rh-catalyzed 1,4-addition reaction to activated olefins and in the Rh-catalyzed hydrogenation of enamide 12, giving the corresponding products with up to 97 and 93% ee, respectively.

A new entry of nucleophiles in rhodium-catalyzed asymmetric 1,4-addition reactions: Addition of organozinc reagents for the synthesis of 2-aryl-4-piperidones

A rhodium-catalyzed asymmetric 1,4-addition reaction has been applied to the synthesis of 2-aryl-4-piperidones. While other conventional nucleophiles fail, organozinc reagents have been successfully utilized for the construction of these useful compounds

Palladium(II)-catalyzed 1,4-addition of arylboronic acids to β-arylenones for enantioselective synthesis of 4-aryl-4H-chromenes

The enantioselective 1,4-addition of arylboronic acids to β-arylenones to give β-diaryl ketones was carried out at 0-25 °C in the presence of a dicationic palladium(II) catalyst, [Pd(S,S-chiraphos)(PhCN) 2](SbF6)2. Additio

The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions

We have designed the first chiral diene-based metal-organic framework (MOF), E2-MOF, and postsynthetically metalated E2-MOF with Rh(i) complexes to afford highly active and enantioselective single-site solid catalysts for C-C bond fo

Enantioselective Hydrogenation of Endocyclic Enones: the Solution to a Historical Problem?

The enantioselective hydrogenation of endocyclic enones has been a historical problem for homogeneous catalysis. We herein report an efficient method to reduce endocyclic enones with molecular hydrogen. Catalyzed by a rhodium/Zhaophos complex, a variety of enones with five-, six- or seven-member ring were hydrogenated with high enantioselectivity (92%—99% ee). Excellent chemo- and enantioselectivity demonstrated this method was successfully applied in the enantioselective hydrogenation of citral to produce enantio-enriched citronellal.

C1-Symmetric Binap Derivative Featuring Single Diferrocenylphosphino-Donor Moiety

A C1-symmetric chiral bisphosphine, FcPh-Binap (1), which possesses a single diferrocenylphosphino moiety together with a conventional Ph2P-substituent, was prepared in enantiomerically pure forms. Ligand 1 is sterically less demanding than Fc-Segphos (A)

Enantioselective Conjugate Addition of Stabilized Arylzinc Iodide to Enones: an Improved Protocol of the Hayashi Reaction

Stabilised arylzinc iodide, prepared by direct insertion of zinc into aryl iodides, were used as nucleophiles in the Hayashi Rh-catalysed enantioselective conjugate addition to enones. The reaction conditions were optimized in the addition of phenylzinc i