39546-79-7

Upstream product

• 20023-43-2 1,1-pentamethylene-1,2-butadiene 
• 70776-29-3 di(tert-butyl)aluminium hydride 
• 30101-37-2 1-Hydroxy-1-pentyl-cyclohexan 
• 42049-47-8 11-iodo-5-undecyne 
• 21406-61-1 pentyltriphenylphosphonium bromide 
• 108-94-1 cyclohexanone 
• 92078-64-3 11-bromo-5-undecyne 
• 141694-59-9 cyclohexylmethane-1,1-diyl bis(trifluoromethanesulfonate) 
• 109-72-8 n-butyllithium 
• 52183-68-3 1-dibromomethyl-1-cyclohexanol 
• 60014-80-4 1-dibromomethyl-1-(trimethylsiloxy)cyclohexane 
• 23904-33-8 (iodomethylene)cyclohexane 
• 2043-61-0 cyclohexanecarbaldehyde 
• 693-02-7 hex-1-yne 

Downstream Products

• 5445-35-2 1-cyclohexyl-1-pentanone 

Relevant academic research and scientific papers

Stereospecific Iron-Catalyzed Carbon(sp2)-Carbon(sp3) Cross-Coupling with Alkyllithium and Alkenyl Iodides

An efficient synthetic protocol involving iron-catalyzed cross-coupling reactions between organolithium compounds and alkenyl iodides as key coupling partners was achieved. More than 30 examples were obtained with moderate to good yields and high stereospecificity. Gram-scale and synthetic applications of this procedure are recorded herein to demonstrate its feasibility and potential utilization.

Catalytic reduction and intramolecular cyclization of haloalkynes in the presence of nickel(I) salen electrogenerated at carbon cathodes in dimethylformamide

Pentylidenecyclopentane can be conveniently prepared in up to 86% yield via the catalytic reduction of 1-iodo- or 1-bromo-5-decyne by [[2,2′-[1,2- ethanediylbis(nitrilomethylidyne)]bis[phenolato]]-N,N′,O,O′] -nickelate(I) electrogenerated at a carbon cathode in dimethylformamide containing tetramethylamnionium tetrafluoroborate. This electrosynthesis can be accomplished at potentials for which the haloalkynes are electroinactive, and it can be completed within 30 min at room temperature. Attempts to synthesize pentylidenecyclobutane and pentylidenecyclohexane from 1-halo-4-nonynes and 11-halo-5-undecynes, respectively, under similar conditions afford the carbocycles in very low yields (2% and 6%, respectively), Other products derived from the various haloalkynes are dimers, alkynes, and 1-alkenynes. Dimers (alkadiynes) arising From 1-halo-4-nonynes and 11-halo-5-undecynes are formed in yields ranging from 80% to 89%, whereas icosa-5, 15-diyne (the dimer obtained from a 1-halo-5-decyne) is found in significantly lower yield (≤ 13%). Alkynes and 1-alkenynes are produced in yields of 3-10% and 2-3%, respectively. A mechanistic scheme, involving alkyn-1-yl radicals arising from niekel(I) salon catalyzed cleavage of the carbon-halogen bond of each haloalkyne, is proposed to account for the formation of all products.

Photoinduced metalation of nonactivated C-Cl bonds with samarium diiodide: Synthesis of alkenes with high (Z)-selectivity through β-elimination reactions

(Chemical Equation Presented) The photoinduced metalation of nonactivated C-Cl bonds of O-acetyl chlorohydrins is promoted by samarium diiodide. As a result of this, β-elimination of O-acetyl chlorohydrins is achieved, affording the corresponding (Z)-alkenes with total or high stereoselectivity.

Synthesis of trisubstituted and tetrasubstituted alkenes via a manganate-induced migration-elimination process

Preparation of alkenes via a manganate-induced alkylation-elimination sequence was investigated. The reaction of 2-alkoxy-1,1-dibromoalkanes with trialkylmanganates afforded disubstituted or trisubstituted alkenes. Treatment of 2-alkoxy-1,1,1-tribromoalkanes with trialkylmanganates provided trisubstituted or tetrasubstituted alkenes through bromine-metal exchange, transfer of two alkyl groups from manganese to carbon, and successive elimination of metal and the β-alkoxy moieties.

Cyclohexynes as intermediates in a novel endo-cyclization of alkynylzincates derived from 5-hexynyl tosylates

The n-type endo-cyclization of metal acetylides to form cyclohexynes was observed for the first time in the reaction of alkynylzincates derived from 5-hexynyl tosylates. The endo-cyclization took place in competition with erocyclization, leading to the formation of 1-(cyclopentylidene)alkylzincs.

Cyclizations during the Grignard Reactions of ω-Bromoalkynes

The Grignard reactions of a number of ω-bromoalkynes have been shown to undergo regioselective cyclizations in certain instances to give the smaller possible carbocycle. These cyclizations are shown to result from two competing processes, whose relative efficiencies depend upon the chain length and the remote substitutent on the acetylene. These are interpreted as a radical cyclization which occurs only during the time the Grignard is being formed from the bromide and an organometallic reaction which slowly transforms the Grignard reagent into its cyclic isomer. The mechanistic details of these transformations are discussed.

Cyclization of α,ω-diborylalkanes via double Suzuki-Miyaura coupling

Both carbo- and heterocyclic six-membered ring systems (3) containing an exocyclic carbon-carbon double bond have been prepared (25-76%) from α,ω-dienes (1) through the cross coupling of their dihydroboration products (2) with either aromatic or aliphatic vinylidene dibromides (4) in a one-pot Pd-catalyzed sequence.

Geminal dialkylation, alkylative reduction and olefination of aliphatic aldehydes. Reaction of gem-bistriflates with higher order dialkylcyanocuprates

gem-Dialkylation or alkylative reduction of α-unbranched aliphatic aldehydes 1 is advantageously achieved by reaction of the corresponding gem-bistriflates 2 with di-n-alkylcyanocuprates or di-sec- and di-tert-alkylcyanocuprates respectively. The reaction of α-branched gem-bistriflates 2 with dialkylcyanocuprates in the presence of boron trifluoride affords the olefins 6 in good yield.

Lewis Acid-Promoted Selective Rearrangement of Trisubstituted Epoxides to Aldehydes or Ketones

Rearrangement of trisubstituted epoxides has been effected under the influence of various Lewis acids.Among these, methylaluminum bis(4-bromo-2,6-di-tert-butylphenoxide) (MABR) can be selectively rearranged from trisubstituted epoxides to aldehydes, while

Synthesis of Alkenes via Peterson Reaction

The α-phenylthiosilanes (2) have been used to prepare the α-silyl anions (1) by reaction with lithium naphthalenide; subsequent condensation with a carbonyl compound gave the alkene (8) via the Peterson reaction.The α-phenylthiosilanes (2) were prepared from n,n-bis(phenylthio)acetals (4) by reaction with lithium naphthalenide and chlorotrimethylsilane.The n,n-bis(phenylthio)acetals (4) were obtained, in turn, from 1,1-bis(phenylthio)acetals (5) by anion formation with butyl-lithium-N,N,N',N'-tetramethylethylenediamine complex in hexane followed by reaction with an alkyl halide.The Peterson reaction was also used to prepare vinyl sulphides (9) and vinyl sulphones (13).