68852-11-9

Upstream product

• 4065-80-9 2-methylenecyclohexanol 
• 1713-33-3 1,2-epoxy-1-methylcyclohexane 
• 1023741-36-7 C₈H₁₄O₄S 
• 108-05-4 vinyl acetate 
• 63268-43-9 (+)-(S)-dimethyl-p-tolylsulfinylmethanephosphonate 
• 4845-04-9 1-cyclohexene-1-methanol 
• 286-20-4 cyclohexene oxide 
• 73766-54-8 (+)-(R)-(1-Cyclohexenylmethyl)-mesityl-sulfoxid 
• 63231-32-3 (-)-(R)-(Cyclohexylidenmethyl)-p-tolyl-sulfoxid 

Relevant academic research and scientific papers

Novel Catalytic Kinetic Resolution of Racemic Epoxides to Allylic Alcohols

(Matrix Presented) The kinetic resolution of racemic epoxides via catalytic enantioselective rearrangement to allylic alcohols was investigated. Using the Li-salt of (1S,3R,4R)-3-(pyrrolidinyl)methyl-2-azabicyclo [2.2.1] heptane 1 as catalyst allowed both

Lipase-catalyzed kinetic resolution of 2-methylene-substituted cycloalkanols in batch and continuous-flow modes

Kinetic resolutions of cyclic racemic secondary alcohols (2-methylenecyclopentan-1-ol rac-1a, 2-methylenecyclohexan-1-ol rac-1b, 2-methylenecycloheptan-1-ol rac-1c, 6-methylene-[1,3]dioxepan-5-ol rac-1d, 2,2-dimethyl-6-methylene-[1,3]dioxepan-5-ol rac-1e and trans-2-bromocyclohexan-1-ol rac-3) catalyzed by different (commercial and in-house-made) lipases were performed using vinyl acetate in THF-hexane. In the most typical cases (rac-1b, rac-1d and rac-3), the immobilized Candida antarctica lipase B (CaLB, for rac-1b and rac-3)- or sol-gel immobilized Pseudomonas fluorescens lipase (sol-gel LAK, for rac-1d)-catalyzed batch mode reactions were compared to the continuous mode reactions carried out in an enzyme-filled stainless steel bioreactor. The effect of temperature (20-60 °C) and flow rate (0.1-0.3 ml min-1) on the continuous-flow acetylation of rac-1b, rac-1d and rac-3 were investigated. In the kinetic resolutions of rac-1b, rac-1d and rac-3, the enantiomeric selectivities (E) were similar in the continuous-flow and batch (shake flask) modes. However, the productivities (specific reaction rate: r), were significantly higher in the continuous-flow mode biotransformations of rac-1b, rac-1d and rac-3.

An efficient procedure for the 1,3-transposition of allylic alcohols based on lithium naphthalenide induced reductive elimination of epoxy mesylates

An efficient protocol for the 1,3-transposition of allylic alcohols has been developed. The method is based on the pretransformation of allylic alcohols into the corresponding epoxy mesylates, followed by the reductive elimination of the resulting epoxy mesylates by using lithium naphthalenide (LN) as a reducing agent. Georg Thieme Verlag Stuttgart.

AlEt3-promoted eliminative ring-opening of β-hydroxy epoxides: Highly stereoselective synthesis of terminal α-hydroxy olefins

AlEt3-promoted eliminative ring-opening of β-epoxy alcohols leading to α-hydroxy olefins is reported. This eliminative ring-opening reaction is shown to be highly stereoselective, thus providing an alternative asymmetric synthesis for α-hydroxy olefins.

Allylic Alcohols by Methylene Transfer from N-Lithiomethyl-N,N',N'',N''-tetramethyldiethylenetriamine to Epoxides

Allylic (homoallylic) alcohols are obtained from epoxides (and certain oxetanes) and N-lithiomethyl-N,N',N'',N''-tetramethyldiethylenetriamine.

A Tellurium Transposition Route to Allylic Alcohols: Overcoming Some Limitations of the Sharpless-Katsuki Asymmetric Epoxidation

Good yields of enantiomeric allylic alcohols can be obtained in high enantiomeric excess (ee) by combining Sharpless-Katsuki asymmetric epoxidation process (SAE) with tellurium chemistry.The advantages of the tellurium process are as follows: (1) the 50percent yield limitation on the allylic alcohol in the Sharpless kinetic resolution (SKR) can be overcome; (2) allylic tertiary alcohols which are unsatisfactory substrates in the SKR can be obtained in high optical purity; (3) optically active secondary allylic alcohols with tertiary alkyl substituents (e.g. tert-butyl) at C-1 can be obtained in high ee; (4) optically active sterically congested cis secondary alcohols can be obtained in high ee; and (5) the nuisance of the slow SAE of some vinyl carbinols can be avoided.The key step in the reaction sequence is either a stereospecific 1,3-transposition of double bond and alcohol functionalities or an inversion of the alcohol configuration with concomitant deoxygenation of the epoxide function in epoxy alcohols.Trans secondary allylic alcohols can be converted to cis secondary allylic alcohols by way of erythro epoxy alcohols (glycidols); threo glycidyl derivatives are converted to trans secondary allylic alcohols.These transformations are accomplished by the action of telluride ion, generated in situ from the element, on a glycidyl sulfonate ester.Reduction of elemental Te is conveniently done with rongalite (HOCH2SO2Na) in an aqueous medium.This method is satisfactory when Te2- is required to attack at primary carbon site of a glycidyl sulfonate.In cases where Te2- is required to attack a secondary carbon site, reduction of the tellurium must be done with NaBH4 or LiEt3BH.Elemental tellurium is precipitated during the course of the reactions and can be recovered and reused.

SOLVOLYTIC HYDROPEROXIDE REARRANGEMENTS IV. Selective Rearrangement of Spirooctan-4-ol.

Rearrangement of spirooctan-4-ol, 1, in acidified THF-H2O2 is a selective process in which substitution occurs with retention of configuration and ring-expansion with inversion of the carbinyl center.

Stereoselective Synthesis of Alcohols, III Stereochemistry of the Sigmatropic Rearrangement of (1-Cycloalkenylmethyl) Sulfoxides

Rearrangement of the chiral allyl sulfoxides 17 and 20 proceeded via the exo-transition state 14 to give the α-methylenecycloalkanols 18 and 21 in high enantiomeric purity.The extent of chirality transferred was less (44 and 60percent) on rearrangement of