77131-98-7

Upstream product

• 77131-93-2 2-Chloro-1-cyclohexyl-but-3-en-1-one 
• 2719-27-9 cyclohexanylcarbonyl chloride 
• 2043-61-0 cyclohexanecarbaldehyde 
• 113662-35-4 (Z-3-chloroprop-2-enyl)tri-n-butyl stannane 
• 107-05-1 3-chloroprop-1-ene 
• 106-95-6 allyl bromide 
• 25203-83-2 (E)/(Z)-buta-1,3-dien-1-ylcyclohexane 

Downstream Products

• 121192-30-1 P--P-methyldibenzophospholium trifluoromethanesulfonate 

Relevant academic research and scientific papers

Simple synthetic method of allyl- and vinyl-epoxides by allylation of carbonyl groups with allylic tins catalyzed by PbI2-HMPA

Allyl epoxides were prepared by the chemoseletive allylation at the carbonyl groups of a-bromo ketones with allylic tin, where PbI2-HMPA effected as a chemoselective catalyst. Moreover, vinyl epoxides were obtained in one pot procedure by the P

Diastereo- and enantioselective synthesis of syn-α-vinylchlorohydrins and cis-vinylepoxides

A new method to generate chiral syn-vinylchlorohydrins and cis-vinyloxiranes is reported. Reaction of (α-haloallyl)lithiums with methoxy-9-BBN or Ipc2BOMe followed by treatment with BF3·OEt2 leads to (Z)-(γ-haloallyl)boranes which react with aldehydes to yield cis-vinylepoxides (de ≥ 90%) upon oxidative workup. Alternatively, addition of ethanolamine to the allylboration product yields syn-α-halohydrins (de ≥ 90%) that are also easily cyclized to cis-vinylepoxides. Extension of this protocol using [(Z)-γ-chloroallyl]BIpc2 leads to chiral syn-α-chlorohydrins and cis-vinylepoxides in high de (≥90%) and ee (90-99%). Enantioselectivity of reactions of chiral (Z)-(γ-chloroallyl)boranes with aldehydes are more sensitive to reaction conditions than enantioselectivity of reactions of other α-or γ-substituted allylboranes. The effects of proportion of BP3·OEt2 and the relative efficacies of LiNR2 bases on diastereo- and enantioselectivity of the chloroallylation are reported.

Reactions of α-haloallyllithium derivatives with carbon, silicon, tin or boron halides and carbonyl compounds

A series of allylic halides have been converted into their α-carbanions with strong lithium bases, using different techniques.These have been compared in their reaction with various electrophiles leading to functionally substituted allyl derivatives.The influence of the counterion on the regio- and stereoselectivity has been investigated. allylic halides / α-halocarbanions / allylsilanes / allyltin derivatives / α-chlorohydrins / vinylepoxides / diastereoselectivity

A FIRST EXAMPLE OF CATALYTIC YLIDE EPOXIDATION REACTION: FACILE SYNTHESIS OF VINYL EPOXIDES FROM ALDEHYDES CATALYZED BY DIISOBUTYL TELLURIDE

In the presence of cesium carbonate, a variety of aldehydes can be epoxidized directly with allyl bromide at 50 deg C under solid-liquid phase transfer condition by use of a catalytic amount of diisobutyl telluride to afford vinyl epoxides in good yields

Kinetic (Not Equilibrium) Factors Are Dominant in Wittig Reactions of Conjugated Ylides

The Wittig reaction of ester-, vinyl-, or benzyl-stabilized ylides is examined in detail.Extensive control experiments have been performed to probe the oxaphosphetane intermediates, and reversal in these systems is ruled out as a significant (>5percent) process.Betaine reversal, on the other hand, can be detected in the control experiments, depending on the conditions.Maximum betaine reversal is associated with formation of the anti betaine rotamers, while syn betaines can be generated in ethanol or THF without significant reversal cases.It is emphasized that betainesare obligatory intermediates in the control experiments, but they are neither obligatory nor likely intermediates in Wittig reactions, especially the E-selective examples conducted in aprotic solvents.Only the oxaphosphetanes are required to describe the overall Wittig process from ylide to alkene.Other intermediates are not necessary, including zwitterions, specific conformers, pseudorotamers, etc.The traditional control experiments are more complex and are shown to involve anti betaines as well as syn betaines (2, 24, 25), and in certain cases, hydroxy ylides (28) derived from the betaines.The E-selective reactions of ester-stabilized ylides are described as asynchronous cycloadditions with a relatively advanced, oxaphosphetane-like transition state.Exceptionally E-selective olefination is achieved using the allylic dibenzophospole ylide 11a.The intermediate oxaphosphetanes 14a, 15a, and 15b are observed for the first time in a conjugated-ylide reaction.

FACILE PREPARATION OF γ-CHLORO-SUBSTITUTED ALLYLMETALLIC REAGENTS AND THEIR REACTIONS. STEREOSELECTIVE ACCESS TO CIS-VINYLOXIRANES

The title compounds are readily prepared from metallated allyl chloride and organotin chloride or organoaluminum chloride.After treatment with a base, they react with aldehydes in highly regio- and diastereo-selective modes, giving cis-vinyloxiranes selectively.Keywords -- lithiated allyl chloride; Z-γ-chloroallyltrimethyltin; γ-chloroallyldiethylaluminum; stereoselective synthesis; syn-chlorohydrin; cis-vinyloxirane

Selective Condensation of titanium Reagent with Carbonyl Compounds

titanium reagent generated easily from allyl ethyl sulfides condensed with aldehydes to give erythro-β-hydroxy sulfides in highly regio- and stereoselective manner.In contrast, crotyl ethyl sulfide reacted with aldehydes affording δ-hydroxy vinyl sulfide exclusively.The substitution pattern of the starting sulfide can have a pronounced effect on the selectivity in this condensation reaction, erythro-β-Hydroxy sulfide obtained was transfromed stereoselectively to the trans-vinyloxirane or 1,3-alkadiene.

Reaction of 3-Chloroallyltrimethylsilane with Acid Chloride and Exploitation of a New Regioselective Synthesis of αβ-Unsaturated Epoxide

α-Chloro-βγ-unsaturated ketone (2) was synthetized from the reaction of 3-chloroallyltrimethylsilane (1) with acid chloride.The ketone was converted into αβ-unsaturated epoxide (3) regioselectively in good yield via reduction with NaBH4 or LiAlH4 followed