140439-82-3

Upstream product

• 5664-17-5 cyclohexylallene 
• 100-52-7 benzaldehyde 
• 141023-05-4 tert-Butyl-((E)-3-cyclohexyl-allyloxy)-dimethyl-silane 
• 141023-06-5 1-tert-butyldimethylsilyloxycyclohex-1-enyl-prop-2-ene 
• 106-96-7 propargyl bromide 
• 110-83-8 cyclohexene 
• 1568-65-6 bis(cyclohexanyl)borane 
• 209607-09-0 (E)-3-chloroprop-1-enyldicyclohexylborane 
• 42134-55-4 (E)-3-cyclohexyl-2-propen-1-ol 

Relevant academic research and scientific papers

Hydroboration of mono-substituted allenes: A general synthetic route to the higher crotylboranes and anti-3-alkyl/aryl-4-hydroxy-1-alkenes

Hydroboration of mono-substituted allenes with Chx2BH at 0°C leads to the corresponding (E)-substituted allylboranes, known as higher crotylboranes, exclusively. These higher crotylboranes react with aldehydes, and on oxidation, provide the cor

The hydroboration of propargyl chloride: A flexible one-pot three-component process easily directed towards the synthesis of (E)-homoallylic alcohols or anti-homoallylic alcohols

The hydroboration of propargyl chloride by means of a dialkylborane affords 3-chloro-propenyl boranes 6 which, in the presence of a quaternary ammonium chloride, rearrange into allylic boranes 9 and 10, precursors of (E)-homoallylic alcohols 7 or anti-homoallylic alcohols 5, respectively. Synthetic protocols for the selective generation of 5 and 7 were developed.

The hydroboration of propargyl bromide. Simple one-pot three-component routes to (Z)-1-bromoalk-1-en-4-ols and to anti-homoallylic alcohols

The hydroboration of propargyl bromide with dialkylboranes takes place regioselectively to give 3-bromoprop-1-en-1-yl dialkylboranes 13 which, upon quaternization with bromide ion, undergo a series of transformations into a number of allylic boron species. By a suitable choice of the experimental conditions it is possible to trap the reaction intermediates with aldehydes and to steer the process toward either the synthesis of (Z)-1-bromoalk-1-en-4-ols 6 or anti-homoallylic alcohols 8. Two one-pot three-component processes were developed based on a sequence of four reactions; preparation of dialkylborane and hydroboration of propargyl bromide are the first steps. Then, quaternization with TEBABr may be carried out either in the presence of the aldehyde when (Z)-1-bromoalk-1-en-4-ols 6 are requested, or in the absence of the aldehyde in order to allow the formation of γ-substituted allyl borane 18 which, successively, adds to the aldehyde affording antihomoallylic alcohols 8.

Highly regioselective and stereoselective allylation of aldehydes via palladium-catalyzed in situ hydrostannylation of allenes

(Equation presented) Highly regio-and stereoselective allylalion of aldehydes by allenes proceeds smoothly in aqueous/organic media in the presence of PdCl2-(PPh3)2, HCl, and SnCl2. The reaction likely occurs via hydrostannylation of allenes and allylation of aldehydes by the in situ generated allyltrichlorotins to afford the final products.

A one-pot three-component route to anti-homoallylic alcohols based on the hydroboration of propargyl bromide

(3-Bromoalken-1-yl)dialkylboranes, generated by hydroboration of propargyl bromide with dialkylboranes, smoothly rearranges to (E)-allylic boranes which can be trapped with aldehydes. The resulting one-pot three- component sequence represents a route to anti-homoallylic alcohols in fairly good yields.

Palladium-catalyzed carbonyl allylation by allylic alcohols with SnCl2

Allylic alcohols can be applied to carbonyl allylation via the formation of π-allylpalladium complexes, using palladium as catalyst and SnCl2 as a reducing agent. This reaction has chemoselectivity: The reactivity order of allylating agents is allylic carbonate > allylic alcohol > allylic acetate, and that of carbonyl compounds is aldehyde > ketone. High regioselcction was observed in polar solvents such as DMF, DMI, and DMSO; carbonyl compounds apparently attacked the more substituted allylic position of π-allylpalladium complexes to afford only one regioisomer. Diastereocontrol in the carbonyl allylation of aromatic aldehydes by (E)-2-butenol was achieved by the choice of polar solvents; use of DMSO at 25 °C led to syn selection, while anti selection was found at -10 °C in THF. The addition of H2O in any solvent accelerated the carbonyl allylation and enhanced both regioselectivity and the diastereoselectivity. Anti selection in DMF, DMI, and THF-H2O can be explained by the chair form of the six-membered cyclic transition state, while syn selection in DMSO allows us to propose an acyclic antiperiplanar transition state. An NMR spectroscope investigation demonstrated that the actual allylating agent in dry medium was allyltrichlorotin: 1H, 13C, and 119Sn NMR spectra of the reaction of allyl alcohol with PdCl2(PhCN)2-SnCl2 in DMF-d7. corresponded to those of the reaction of allyl chloride with PdCl2(PhCN)2-SnCl2 in DMF-d7.

Preparation and Regio- and Diastereoselective Reactions of Allylic Zirconium Reagents from Allylic Ether Derivatives

Allylic zirconium reagents were generated by treating allylic ether derivatives with zirconocene "Cp2Zr".The allylic zirconium reagents reacted with aldehydes in highly regio- and diastereoselective manner to give homoallylic alcohol compounds. Key Words: zirconocene; zirconacycles; allylic ether derivatives; allylic zirconium reagent; homoallylic alcohol derivatives

Organoborane-Catalyzed Hydroalumination of Terminal Allenes

Organoborane-catalyzed hydroalumination of terminal allenes with dichloroaluminum hydride gives rise to the corresponding allylaluminum compounds under mild conditions with high regioselectivity.