42437-24-1

Upstream product

• 98-53-3 4-tercbutyl-cyclohexanone 
• 1730-25-2 allylmagnesium bromide 
• 106-95-6 allyl bromide 
• 556-56-9 allyl iodid 
• 19206-69-0 allyl diphenyl phosphate 
• 1469-70-1 allyl ethyl carbonate 
• 105750-96-7 1-allyl-4-tert-butyl-1-trimethylsiloxycyclohexane 
• 107-05-1 3-chloroprop-1-ene 
• 140901-88-8 4-tert-Butyl-1,1-bis<(2-propenyl)oxy>cyclohexan 
• 2622-05-1 allylmagnesium bromide 
• 140901-91-3 cis-4-tert-Butyl-1-(phenylseleno)-1-(2-propenyloxy)cyclohexan 
• 140901-90-2 trans-4-tert-Butyl-1-(phenylseleno)-1-(2-propenyloxy)cyclohexan 
• 75863-14-8 2-Propenyltitanium triisopropoxide 
• 6928-75-2 diallylmagnesium 

Downstream Products

• 27557-56-8 cis-t-butyl-4 propyl-1 cyclohexanol 
• 63474-26-0 (E)-c-4-t-butyl-t-1-prop-1'-enylcyclohexan-r-1-ol 

Relevant academic research and scientific papers

Ti/Ni-based multimetallic system for the efficient allylation of carbonyl compounds

A mild method for the allylation of carbonyl compounds is presented. This methodology allows the allylation of a broad range of carbonyl compounds starting with allyl carbonates as pronucleophiles. Noteworthy is that ketones, infrequent substrates in other related protocols, are suitable substrates under these reaction conditions. Moreover, the reaction proceeds at room temperature with the use of catalytic amounts of both Ni and Ti catalysts. The success of this strategy is based on the perfect match between the late transition metal (nickel) and the radical reagent (titanium). The use of Ni instead of Pd widens the scope of this transformation and makes this method more economical.

Stereoselective alkene isomerization over one position

Although controlling both the position of the double bond and E:Z selectivity in alkene isomerization is difficult, 1 is a very efficient catalyst for selective mono-isomerization of a variety of multifunctional alkenes to afford >99.5% E-products. Many reactions are complete within 10 min at room temperature. Even sensitive enols and enamides susceptible to further reaction can be generated. Catalyst loadings in the 0.01-0.1 mol% range can be employed. E-to-Z isomerization of the product from diallyl ether was only -6 times as fast as its formation, showing the extremely high kinetic selectivity of 1.

Mesoporous aluminosilicate-catalyzed allylation of carbonyl compounds and acetals

A mesoporous aluminosilicate (Al-MCM-41) was found to be an effective heterogeneous catalyst for the reaction of both carbonyl compounds and acetals with allylsilanes to afford the corresponding homoallyl silyl ethers and homoallyl alkyl ethers, respectively. Both the mesoporous structure and the presence of aluminum moiety were indispensable for the high catalytic activity of Al-MCM-41. Moreover, Al-MCM-41 could catalyze the reaction of acetals chemoselectively in the presence of the corresponding carbonyl compounds. The solid acid catalyst Al-MCM-41 could be recovered easily by filtration and could be reused three times without a significant loss of catalytic activity.

Ti-catalyzed Barbier-type allylations and related reactions

Titanocene(III) complexes, easily generated in situ from commercial Ti IV precursors, catalyze Barbiertype allylations, intramolecular crotylations (cyclizations), and prenylations of a wide range of aldehydes and ketones. The reaction displays surprising and unprecedented mechanistic subtleties. In cyclizations a fast and irreversible addition of an allyl radical to a TiIII-coordinated carbonyl group seems to occur. Intermolecular additions to conjugated aldehydes proceed through a coupling of a Ti IV-bound ketyl radical with an allyl radical. Reactions of ketones with allylic halides take place by the classical addition of an allylic organometallic reagent. The radical coupling processes enable transformations such as the highly regioselective α-prenylation that are otherwise difficult to achieve. The mild reaction conditions and the possibility to employ titanocene complexes in only catalytic quantities are highly attractive features of our protocol. These unusual properties have been taken advantage of for the straightforward synthesis of the natural products rosiridol, shikalkin, and 12-hydroxysqualene.

Allylation and crotylation of ketones and aldehydes using potassium organotrifluoroborate salts under lewis acid and montmorillonite k10 catalyzed conditions

Two convenient highly diastereoselective protocols for the allylation and crotylation of ketones using practical, air- and water-stable potassium allyl and crotyltrifluoroborate salts have been developed. BF3-OEt 2 and montmorillonit

Evaluation of Chelation Effects Operative during Diastereoselective Addition of the Allylindium Reagent to 2- And 3-Hydroxycyclohexanones in Aqueous, Organic, and Mixed Solvent Systems

The unprotected 2- and 3-hydroxycyclohexanones 1-8 were prepared by methods that skirted as much as possible their proclivity for α-ketol rearrangement (where the possibility for such isomerization exists). The diastereofacial selectivity of their reactio

Ligand effects in selective addition reactions of organoindium reagents with carbonyl compounds

The reaction of the allyl indium sesquibromide (CH2 =CHCH2)3In2Br3 with four equivalents of a bulky lithium alkoxide ((CH3)3COLi or (CH3)3CCH2OLi) results in modified reagents which show unusual degrees of chemo-and stereoselectivity in reactions with carbonyl compounds. For example, in reactions with cyclohexanone derivatives, 84-93% equatorial attack with preferential formation of the axial alcohols is observed. Chiral aldehydes react in a highly diastereoselective manner.

First preparation of allyl vanadium reagents in a mixed solvent of THF and HMPA (HMPA = hexamethylphosphoric triamide) and their application to allylation of carbonyl compounds

Allylation of carbonyl compounds with allyl bromide mediated by a vanadium(II) complex in a mixed solvent of THF and HMPA (HMPA = hexamethylphosphoric triamide) has been accomplished. Coordination of HMPA to a vanadium metal is essential for the stabilization of the allyl vanadium species.

A Novel Entry into Wittig Rearrangements - A Stereoselective -Wittig Rearrangement with Inversion of Configuration at the Carbanion Center

The O,Se ketal 10, through lithium naphthalenide induced reductive cleavage of its Csp3-Se bond, was converted into the α-lithio ether 11a with an equatorially oriented C-O bond.At -78 deg C, 11a undergoes a rapid -Wittig rearra

Samarium(II) Di-iodide Induced Reductive Coupling of α,β-Unsaturated Esters with Carbonyl Compounds Leading to a Facile Synthesis of γ-Lactone

Samarium(II) di-iodide, which is a strong one-electron transfer reducing agent, is effective for the reductive coupling of α,β-unsaturated esters with carbonyl compounds, whereby substituted γ-lactones can easily be prepared in good to excellent yields under very mild conditions.Two mole equiv. of samarium(II) di-iodide to each mole equiv. of starting substrate always give reasonable yields.The presence of an alcohol is essential in the reaction, complex unidentified products being formed in the absence of an alcohol; t-butyl alcohol gave more satisfactory results than methanol and ethanol.The alcohol acts as a proton donor, the use of MeOD leading to a deuteriated γ-lactone.The reaction is applicable to both aliphatic and aromatic ketones or aldehydes, whereas the electrochemical method is limited to aliphatic substrates.The diastereoselectivity is examined in the reaction of 4-t-butylcyclo-hexanone with ethyl acrylate; an anti-isomer is produced predominantly (syn:anti = 1:9) as the result of selective axial attack.The reaction may proceed by a radical mechanism, and reaction may not involve a samarium ester homoenolate.The reaction is extended to the intramolecular reaction of an α,β-unsaturated keto ester (8-oxonon-2-enoate) leading to the ready synthesis of a bicyclic γ-lactone.