103532-78-1

Basic information

• Product Name: Cyclohexanol, 2,2-dimethyl-, (1S)-
• CAS NO: 103532-78-1
• Molecular Formula: C8H16O
• Molecular Weight: 128.214
• Mol File: 103532-78-1.mol

Chemical Properties

• CAS DataBase Reference: Cyclohexanol, 2,2-dimethyl-, (1S)-(CAS DataBase Reference)
• NIST Chemistry Reference: Cyclohexanol, 2,2-dimethyl-, (1S)-(103532-78-1)
• EPA Substance Registry System: Cyclohexanol, 2,2-dimethyl-, (1S)-(103532-78-1)

Safety Data

• Hazardous Substances Data: 103532-78-1(Hazardous Substances Data)

Upstream product

• 1193-47-1 2,2-dimethyl-cyclohexanone 
• 131206-73-0 (+)-(S)-4-Hydroxy-3,3-Dimethyl-1-cyclohexanone 
• 131206-72-9 2,2-Dimethylcyclohexane-1,4-dione 
• 123196-48-5 (+/-)-2,2-Dimethyl-4-tetrahydropyranyloxy-1-cyclohexanone 
• 123214-39-1 (+/-)-4-Hydroxy-2,2-dimethyl-1-cyclohexanone 

Relevant articles and documents

Chiral Synthesis via Organoboranes. 15. Selective Reductions. 42. Asymmetric Reduction of Representative Prochiral Ketones with Potassium 9-O-(1,2:5,6-Di-O-isopropylidene-α-D-glucofuranosyl)-9-boratabicyclononane

Potassium 9-O-(1,2:5,6-di-O-isopropylidene-α-D-glucofuranosyl)-9-boratabicyclononane (9-O-DIPGF-9-BBNH, K-glucoride), a new stable chiral borohydride reducing agent, was prepared by reaction of the corresponding borinic ester, 9-O-DIPGF-9-BBN, with potassium hydride in THF.The reagent provides high optical induction for asymmetric reduction of prochiral ketones, such as relatively hindered aliphatic ketones, alkyl aromatic ketones, and α-keto esters.In particular, the reduction of hindered α-keto esters provides the corresponding α-hydroxy esters with optical purities approaching 100percent ee.Moreover, the reduction of relatively hindered aliphatic ketones such as 3,3-dimethyl-2-butanone, 2,2-dimethylcyclopentanone, spirononan-1-one, and 2,2-dimethylcyclohexanone yields the corresponding alcohols in 70percent ee, 84percent ee, 82percent ee, and 64percent ee, respectively.The reduction of unhindered aliphatic ketones such as 2-butanone, 3-methyl-2-butanone, 2-octanone, and cyclohexyl methyl ketone provides the corresponding alcohols in relatively low optical purities, 3percent ee, 39percent ee, 27percent ee, and 23percent ee respectively.Alkyl aromatic ketones are reduced to the corresponding alcohols, providing products in 78percent ee for acetophenone, 92percent ee for propiophenone, 87percent ee for butyrophenone, 87percent ee for isobutyrophenone, 85,4percent ee for valerophenone, 97-100percent ee for pivalophenone, and 91percent ee for 2'-methylacetophenone.The reduction of α-keto esters provides the corresponding α-hydroxy esters in exceptionally high ee, such as 86percent ee for methyl pyruvate, 86percent ee for ethyl pyruvate, 87percent ee for isopropyl pyruvate, 81percent ee for tert-butyl pyruvate, 92percent ee for ethyl 2-oxobutanoate, 94percent ee for ethyl 2-oxopentanoate, 98percent ee for methyl 3-methyl-2-oxobutanoate, 97percent ee for ethyl 3-methyl-2-oxobutanoate, 97percent ee for methyl 3,3-dimethyl-2-oxobutanoate, 98percent ee for ethyl 3,3-dimethyl-2-oxobutanoate, 93percent ee for ethyl 4-methyl-2-oxopenyanoate, 92percent ee for methyl benzoylformate, 94percent ee for ethyl benzoylformate, 93percent ee for isopropyl benzoylformate, and 96percent ee for ethyl α-oxo-1-naphthaleneacetate.The reduction of relatively more hindered ketones such as 3,3-diethyl-2-pentanone, 2,2,2-triphenylacetone, 2,2,2-triethylacetophenone, 2,2,2-triphenylacetophenone, and 2',4',6'-trimethylacetophenone results in a serious decrease in optical purity, 25percent ee, 7percent ee, 34percent ee, 4percent ee, and 35percent ee, respectively. 4-Chlorobenzophenone is reduced to 4-chlorobenzhydrol in only 11,5percent ee.Ethyl 2,2-dimethylacetoacetate is reduced to ethyl 2,2-dimethyl-3-hydroxybutanoate in 43percent ee.The reductions of alkyl heterocyclic ketones such as 2-acetylfuran, 2-acetylthiophene, and 3-acetylpyridine afford the corresponding alcohols with 42percent ee, 42percent ee, and 70percent ee, respectively.The reductions of α-halo ketones, 2-chloroacetophenone and 2,2,2-trifluoroacetophenone, yield the corresponding halohydrins in 77percent ee and 48percent ee, respectively. trans-4-Phenyl-3-buten-2-one is reduced to the corresponding allylic alcohol in 60percent ee.The reduction of 4-phenyl-3-butyn-2-one provides the corresponding acetylenic alcohol in 61percent ee.The ...

Asymmetric hydrogenation of tert-alkyl ketones: DMSO effect in unification of stereoisomeric ruthenium complexes

Face off: The ruthenium complexes of a new axially chiral PNNligand (L) are highly efficient in the presence of dimethylsulfoxide (DMSO) for hydrogenation of both functionalized and unfunctionalized tert-alkyl ketones. DMSO is thought to narrow down the many possible complex stereoisomers into a single facial L/Ru complex, thus enhancing the reactivity, selectivity, and productivity. Copyright

RUTHENIUM COMPLEX AND PROCESS FOR PRODUCING TERT-ALKYL ALCOHOL THEREWITH

A tert-alkyl ketone, pinacolone was hydrogenated under pressurized hydrogen in the presence of a ruthenium complex (S)-1 and a base, and corresponding (S)-3,3,-dimethyl-2-butanol was thereby obtained in 100% yield and 97% ee.

Asymmetric hydrogenation of tert-alkyl ketones

A combined system of RuCl2(tolbinap)(pica) and an alkaline or organic phosphazene base catalyzes asymmetric hydrogenation of sterically congested tert-alkyl ketones (TolBINAP = 2,2-bis(di-4-tolylphosphino)-1,1-binaphthyl, PICA = α-picolylamine). Hydrogenation with RuH(η1-BH4)(tolbinap)(pica) does not require any strong base. Alcoholic solvents strongly affect the catalytic efficiency. The reaction proceeds smoothly in ethanol under 1-20 atm of H2 and at room temperature with a substrate to catalyst molar ratio of up to 100000. Various aliphatic, aromatic, heteroaromatic, and olefinic tert-alkyl ketones are convertible to the corresponding chiral carbinols in high enantiomeric purity. Olefinic and heteroaromatic functions are left intact. Certain cyclic ketones are also usable. The mode of enantioface selection is consistent and predictable. Copyright

Asymmetric hydrosilylation of ketones using trans-chelating chiral peralkylbisphosphine ligands bearing primary alkyl substituents on phosphorus atoms

Asymmetric hydrosilylation of simple ketones with diphenylsilane proceeded at -40 °C in the presence of a rhodium complex (0.001 - 0.01 molar amount) coordinated with a trans-chelating chiral bisphosphine ligand bearing linear alkyl substituents on the phosphorus atoms, (R,R)-(S,S)-Et-, Pr-, or BuTRAP, giving the corresponding optically active (S)- secondary alcohols with up to 97% ee. The asymmetric hydrosilylation using TRAP ligands with bulkier P-substituents resulted in much lower enantioselectivities. The EtTRAP-rhodium catalyst was also effective for asymmetric hydrosilylation of keto esters with a coordination site for a rhodium atom (up to 98% ee). Optically active symmetrical diols were obtained with up to 99% ee from the corresponding diketones via the asymmetric reduction using 2.5 molar amounts of diphenylsilane.

Enzymatic Preparation of Chiral 4-Hydroxy-2,2-dimethyl-1-cyclohexanone as a Chiral Building Block

(S)-4-Hydroxy-2,2-dimethyl-1-cyclohexanone (1a) was prepared by two enzymatic methods. 1,4-Cyclohexanediol was converted to monoacetal (11) via (+/-)-1a.Enzymatic reduction of 11 by baker's yeast gave (S)-1 of almost 100 percent e.e.Direct hydroxylation of 2,2-dimethyl-1-cyclohexanone (14) by P-450 camphor monooxygenase of the cloned genes of Pseudomonas putida PpG1 gave (S)-1a of almost 100 percent e.e., too.According to Mitsunobu's method, SN-2 inversion of (S)-1 gave (R)-1.

Chiral Synthesis via Organoboranes. 14. Selective Reductions. 41. Diisopinocampheylchloroborane, an Exceptionally Efficient Chiral Reducing Agent

Diisopinocampheylchloroborane, readily prepared in both enantiomers in high chemical and optical purities (99percent ee) via hydroboration followed by treatment with dry hydrogen chloride in ethyl ether, reduces prochiral ketones at convenient rates in tetrahydrofuran at -25 deg C.Reduction of simple dialkyl ketones, 2-butanone, 2-octanone, and 3-methyl-2-butanone, yields the corresponding alcohols with 4percent, 7percent, and 32percent optical induction.On the other hand, aralkyl ketones are reduced with very high asymmetric induction.Thus, acetophenone, propiophenone, butyrophenone, and decanophenone are reduced with 98percent, 98percent, and 97percent ee, respectively.Branching of the alkyl chain diminishes the induction.Isobutyrophenone and pivalophenone are reduced in 78percent and 79 ee, respectively.Functional groups in the aromatic ring are not affected by the reagent and do not appear to influence significatly the optical yield realized.Thus, 2',5'-dimethoxypropiophenone is reduced in 96percent ee. 1-Indanone and α-tetralone are reduced in 98percent and 87percent ee, respectively. 2'-Acetonaphthone is reduced in 98percent ee.Heteroaryl alkyl ketones are also reduced with excellent optical induction.Thus, 3-acetylpyridine and 2-acetylthiophene are reduced in 92percent and 91percent ee, respectively.The reagent reduces α-tertiary aliphatic ketones under neat condition at room temperature with very high optical induction. 3,3-Dimethyl-2-butanone, ethyl 2,2-dimethylacetoacetate, 2,2-dimethylcyclopentanone, 2,2-dimethylcyclohexanone, and spirononan-1-one are reduced to the corresponding alcohols in 95percent, 84percent, 98percent, 91, and 95percent ee, respectively.Some α,β-unsaturated ketones are reduced with lesser optical induction, such as 4-phenyl-3-butyn-2-one and 2-cyclohexenone, which are reduced to the alcohols in 21 and 36percent ee respectively.On the other hand, trans-4-phenyl-3-buten-2-one is reduced to the alcohol.Certain α-keto esters are reduced in 50-70percent ee.The mechanism of the reduction is postulated to be via a six-membered cyclic "boatlike" transition state.X-ray crystal structure data for the reagent are presented.

Highly Efficient Asymmetric Reduction of α-Tertiary Alkyl Ketones with Diisopinocampheylchloroborane

(-)-Diisopinocampheylchloroborane, which reduces many aralkyl and heteroaralkyl ketones with remarkably high stereoselectivity, has now been found to reduce α-tertiary alkyl ketones with similar high enantiomeric excess.Such ketones have resisted asymmetr