15341-64-7

Upstream product

• 18229-79-3 3-Cyclohexen-⁽¹⁾-yl-propin-⁽²⁾-al-⁽¹⁾-diethylacetal 
• 17497-53-9 1-iodo-1-cyclohexene 
• 107-19-7 propargyl alcohol 
• 19012-03-4 N-methyl-3-formylindole 
• 931-49-7 1-ethenylcyclohexene 
• 68-12-2 N,N-dimethyl-formamide 
• 109-94-4 formic acid ethyl ester 

Downstream Products

• 127915-51-9 ethyl (E)-5-(1-cyclohexen-1-yl)-2-penten-4-ynoate 
• 1232144-26-1 (S)-methyl-3-(6-((tert-butyldimethylsilyloxy)methyl)-3-hydroxy-4-oxo-4H-pyran-2-yl)-3-cyclohexenylpropanoate 
• 1326217-71-3 (4R)-2-cyclohex-1-enyl-4-hydroxy-4H-chromene-3-carbaldehyde 
• 1383738-65-5 (S)-2-tert-butyl-5-(cyclohex-1-en-1-yl)-3-phenyl-2,3-dihydroisoxazole-4-carbaldehyde 
• 1413810-33-9 tert-butyl 4-cyclohexenyl-2-hydroxybut-3-ynyl(furan-2-yl)-carbamate 
• 1610597-73-3 (Z)-3-(cyclohex-1-en-1-yl)-3-(dimethyl(phenyl)silyl)acrylaldehyde 
• 1610597-72-2 (E)-3-(cyclohex-1-en-1-yl)-3-(dimethyl(phenyl)silyl)acrylaldehyde 
• 1402404-47-0 1-(5-(cyclohex-1-en-1-yl(triethylsilyl)methyl)-2-methylfuran-3-yl)ethanone 
• 15341-65-8 1--4-carbethoxy-hexen-(3)-in-(1)-on-(5) 

Relevant academic research and scientific papers

Copper-Catalyzed Asymmetric Silylation of Propargyl Dichlorides: Access to Enantioenriched Functionalized Allenylsilanes

A copper-catalyzed silylation of propargyl dichlorides was developed to access chloro-substituted allenylsilanes under mild reaction conditions. Moreover, enantioenriched chloro-substituted allenylsilanes can be synthesized in moderate to high yields and good enantioselectivities with this protocol.

Gold-Catalyzed Synthesis of 2,5-Disubstituted Oxazoles from Carboxamides and Propynals

2,5-Disubstituted oxazoles are synthesized by oxidative gold catalysis. In contrast to a reported procedure that delivers 2,4-disubstituted oxazoles starting from terminal alkynes, a switch in selectivity towards a 2,5-disubstitution is achieved by the use of propynals as starting materials. In the new reaction, the key intermediate is formed by the nucleophilic attack of the carboxamide onto a gold carbenoid, and then condensates with the more electrophilic aldehyde moiety already present in the substrate and not with the ketone that is derived from the oxygen donor. This new cyclization mode introduces a new carbonyl moiety as substituent at the 2,5-disubstituted oxazole, an attractive motive that can be found in bioactive compounds or be used for further derivatizations. (Figure presented.).

Reactivity of indole-3-alkoxides in the absence of acids: Rapid synthesis of homo-bisindolylmethanes

An unprecedented behaviour of in situ generated indole-3-alkoxides (MgX or Li) has been reported. Tuning the electronic properties of the alkoxides offered the direct and selective construction of bisindolylmethanes and indole-3-carbinols. This process shows very broad scope and represents the reagent (external) free, greener synthesis of structurally divergent bisindolylmethanes.

Copper(II)-catalyzed silylation of activated alkynes in water: Diastereodivergent access to E- or Z-β-silyl-α,β-unsaturated carbonyl and carboxyl compounds

Copper(II)-catalyzed silylation of substituted alkynylcarbonyl compounds was investigated. Through the activation of Me2PhSiBpin in water at room temperature and open atmosphere, vinylsilanes conjugated to carbonyl groups are synthesized in high yield. A surprising diastereodivergent access to olefin geometry was discovered using a silyl conjugate addition strategy: aldehydes and ketones were Z selective while esters and amides were exclusively transformed into the E products. Dial a diastereomer: The title reaction proceeds through the activation of Me2PhSiBpin in water at room temperature and open atmosphere to produce high yields of vinylsilanes conjugated to carbonyl groups. A surprising diastereodivergent access to olefin geometry was discovered using this silyl conjugate addition strategy: aldehydes were Z selective while esters and amides exclusively delivered the E-configured products.

Copper-Catalyzed Propargylic Substitution of Dichloro Substrates: Enantioselective Synthesis of Trisubstituted Allenes and Formation of Propargylic Quaternary Stereogenic Centers

An easy and versatile Cu-catalyzed propargylic substitution process is presented. Using easily prepared prochiral dichloro substrates, readily available Grignard reagents together with catalytic amount of copper salt and chiral ligand, we accessed a range of synthetically interesting trisubstituted chloroallenes. Substrate scope and nucleophile scope are broad, providing generally high enantioselectivity for the desired 1,3-substitution products. The enantioenriched chloroallenes could be further transformed into the corresponding trisubstituted allenes or terminal alkynes bearing all-carbon quaternary stereogenic centers, through the copper-catalyzed enantiospecific 1,1/1,3-substitutions. The two successive copper-catalyzed reactions could be eventually combined into a one-pot procedure and different desired allenes or alkynes were obtained respectively with high enantiomeric excesses.

An SN2′ displacement approach to allenyl acetates

Reaction of cuprates derived from R3MgBr/CuI/LiBr (R3 = n-alkyl) with R1CCCH(O2CR2)2 (R1 = sp2 hybridised substituent, R2 = mainly Me, alkyl, Ph) provides access to allenyl esters R1R 3CCCH(O2CR2) (51-88%). Such species are not accessible via rearrangement of precursor propargylic R1R 3C(O2CR2)CCH.

From amino acids to Dihydrofurans: Functionalized allenes in modern organic synthesis

In this account, recent accomplishments in the field of target-oriented synthesis involving allenes are summarized. Allenic α-amino acid derivatives 9, which are of interest as possible vitamin B6 decarboxylase inhibitors, were prepared by 1,6-addition of the cyano-Gilman reagent t-Bu2CuLi-LiCN to 2-amino-substituted enynoates 8, and selective deprotection at either the amino or the ester group was realized. 2,5-Dihydrofurans 18 were obtained by cyclization of the corresponding α-hydroxyallenes; for this step, new methods (treatment with hydrogen chloride gas or acidic ion exchange resin; gold(III)-chloride catalysis) were developed. The 2-hydroxy-3,4-dienoates 14 were obtained by diastereoselective oxidation of titanium enolates formed from 3,4-dienoates 12 with dimethyl dioxirane (DMDO), whereas hydroxyallenes 16 were prepared by copper-mediated SN2′-substitution of propargylic epoxides 15.

Synthesis of vinylallenes by conjugate 1,6-, 1,8-, 1,10- and 1,12-addition reactions of organocuprates with acetylenic Michael acceptors and their use as dienes in intermolecular Diels-Alder reactions

Various vinylallenes were synthesized by conjugate cuprate additions to acetylenic Michael acceptors. Thus, 1,6-addition reactions with 2-en-4-ynoates 1, 3, and 5a, respectively, furnished vinylallenes 2, 4, and 7 after regioselective electrophilic capture of the allenyl enolates formed. Likewise, 1,8-addition to 2,4-dien-6-ynoates 8a and 10 gave the vinylallenes 9 and 11, whereas the 1,10-addition of Me2CuLi to 2,4,6-trien-8-ynoate 12 provided allene 13, and the analogous 1,12-addition to 2,4,6,8-tetraen-10-ynoate 14 furnished the polyene 15. These vinylallenes are valuable dienophiles in regio- and stereoselective Diels-Alder reactions, as evidenced by the formation of the cycloaddition products 16-24. In the presence of Lewis acids, vinylallene 4a presumably rearranges to a cyclopentadiene derivative which then forms the cycloadducts 25 and 26. VCH Verlagsgesellschaft mbH, 1996.