82936-58-1

Upstream product

• 13757-08-9 1-(1-hydroxycyclohexyl)-1,3-butadiyne 
• 931-49-7 1-ethenylcyclohexene 
• 85678-39-3 1-[4-(trimethylsilyl)-1,3-butadiyn-1-yl]cyclohexene 
• 108-94-1 cyclohexanone 
• 352296-86-7 6-(cyclohex-1-en-1-yl)-2-methylhexa-3,5-diyn-2-ol 

Downstream Products

• 82936-59-2 1-(1-cyclohexenyl)-1,3-butanedione 
• 1394290-90-4 1-(6,6,6-trifluorohexa-1,3-diyn-1-yl)cyclohex-1-ene 
• 74751-57-8 di-cyclohex-1-enyl-octatetrayne 
• 1415638-84-4 N-(5-(cyclohex-1-en-1-yl)-1-phenylpenta-2,4-diyn-1-yl)-4-methylbenzenesulfonamide 
• 1380540-05-5 C₂₇H₂₂F₄N₂O₂ 
• 1370017-56-3 1-(4-fluorobuta-1,3-diynyl)cyclohex-1-ene 
• 1314872-22-4 (R)-5-cyclohexenyl-1-cyclohexylpenta-2,4-diyn-1-ol 
• 1314872-09-7 (R)-5-cyclohexenyl-1-phenylpenta-2,4-diyn-1-ol 

Relevant academic research and scientific papers

Syntheses of trifluoroethylated unsymmetrical 1,3-diynes by using 1,1-dichloro-2,2,2-trifluoroethane

Copper-mediated reaction of terminal 1,3-diynes with 1,1-dichloro-2,2,2-trifluoroethane (CF3CHCl2) using ethanolamine as ligand gave trifluoroethylated unsymmetrical 1,3-diynes in moderate to good yields. The reaction were carried out under mild conditions, and were easy to operate. Aryl groups with weak electron-withdrawing group or electron-donating group, and alkyl substitutents at terminal 1,3-diynes were tolerated. Synthesis of a trifluoroethylated conjugated triyne by using this method was demonstrated. Further transformation of the trifluoroethylated unsymmetrical 1,3-diyne to provide trifluoroethyl-substituted 1,2,3-triazole and isoxazole as application examples were successfully realized.

Mori-Hiyama versus hay coupling for higher polyynes

Dimerizations of C4 precursors RCa=CCa=CTMS [R = C 6H5 (1), p-CH3C6H5, (2), 4-n-C5H11C6H4 (3), C 6H9 (4), p-CH3O

Zinc-mediated enantioselective addition of terminal 1,3-diynes to N-arylimines of trifluoropyruvates

A facile and effective enantioselective addition of terminal 1,3-diynes to acyclic α-CF3 ketimine esters has been developed by using zinc/Binol complexes. The reaction works well with a variety of aromatic-, aliphatic- and silyl-substituted diynes, providing the desired products in up to 97% yield and 97% enantiomeric excess.

From highly enantioselective catalytic reaction of 1,3-diynes with aldehydes to facile asymmetric synthesis of polycyclic compounds

(S)-1,1′-Binaphth-2-ol (BINOL) in combination with ZnEt2, Ti(OiPr)4, and biscyclohexylamine was found to catalyze the highly enantioselective (83-95% ee) addition of various 1,3-diynes to aldehydes of diverse structures. This method provides a convenient pathway to generate a number of optically active dienediynes as the acyclic precursors to polycyclic compounds. The chiral dienediynes undergo highly chemoselective Pauson-Khand (PK) cycloaddition in benzaldehyde by using [Rh(cod)Cl]2 as the catalyst in the presence of rac-BINAP. High diastereoselectivity (up to >20:1) has also been achieved with the chiral dienediyne substrates containing a bulky substituent adjacent to the chiral center. In the presence of the Grubbs II catalyst, ring-closing enyne metathesis of the PK cycloaddition products led to the formation of the desired 5,5,7- and 5,5,8-fused tricyclic compounds. Further highly diastereoselective Diels-Alder reaction of a 5,5,7-tricyclic compound with maleic anhydride produced a 5,5,7,6-polycyclic product. The asymmetric synthesis of polycyclic compounds from optically active dienediynes has established a novel and efficient synthetic route to the structural framework of many biologically significant molecules.

Enantioselective prophenol-catalyzed addition of 1,3-diynes to aldehydes to generate synthetically versatile building blocks and diyne natural products

A highly enantioselective method for the catalytic addition of terminal 1,3-diynes to aldehydes was developed using our dinuclear zinc ProPhenol (1) system. Furthermore, triphenylphosphine oxide was found to interact synergistically with the catalyst to substantially enhance the chiral recognition. The generality of this catalytic transformation was demonstrated with aryl, α,β-unsaturated and saturated aldehydes, of which the latter were previously limited in alkynyl zinc additions. The chiral diynol products are also versatile building blocks that can be readily elaborated; this was illustrated through highly selective trans-hydrosilylations, which enabled the synthesis of a β-hydroxyketone and enyne. Additionally, the development of this method allowed for the rapid total syntheses of several biologically important diynol-containing natural products.

Synthesis of (Z)-1-organylthiobut-1-en-3-ynes: Hydrothiolation of symmetrical and unsymmetrical buta-1,3-diynes

Hcny BRAdrothiolation of l-organcny BRAlbuta-l,3-dicny BRAnes and 1,4-diorgancny BRAlbuta-l,3-dicny BRAnes with the sodium organcny BRAlthiolate anions, which were generated in situ bcny BRA reacting diphencny BRAl and dibutcny BRAl disulfide with NaBHsu

A modular approach to α-arylated carbonyl compounds via indium tris(bistriflylamide)-catalyzed regioselective addition of β-ketoesters to 1,3-diynes

A modular synthesis of α-arylated carbonyl compounds has been achieved by the combination of an indium-catalyzed regioselective addition of β-keto esters to conjugated diynes and a palladium-catalyzed benzannulation reaction. Indium tris(bistriflylamide),

Synthesis of (Z)-1-phenylseleno-1,4-diorganyl-1-buten-3-ynes: Hydroselenation of symmetrical and unsymmetrical 1,4-diorganyl-1,3-butadiynes

The hydroselenation of 1-organyl-1,3-butadiynes and 1,4-diorganyl-1,3-butadiynes with the sodium phenylselenolate anion, which was generated in situ by reacting diphenyl diselenide with NaBH4 in aqueous ethanol, results in the regio-, stereo- and chemoselective formation the 1-phenylseleno-4-organyl-1-buten-3-ynes and 1-phenylseleno-1,4-diorganyl-1-buten-3-ynes of Z configuration respectively. The lack of selectivity with the 2-hydroxy-2-methyl-3,5-dodecadiyne was observed and the obtained product structures were studied in detail.

Hydration of Diacetylene Compounds. Synthesis of a Marine Natural Product: (+/-)-1-(2,6,6-Trimethyl-4-hydroxycyclohexenyl)-1,3-butanedione

The marine natural product (+/-)-1-(2,6,6-trimethyl-4-hydroxycyclohexenyl)-1,3-butanedione (1) was synthesized from known the keto alcohol 3 and 1,4-dichlorobut-2-yne.The synthetic sequence involves dehydration of the diyne tertiary alcohol 2 and hydratio

SYNTHESIS OF (+/-)-1-(2,6,6-TRIMETHYL-4-HYDROXYCYCLOHEXENYL)-1,3-BUTANEDIONE (1), A MARINE NATURAL PRODUCT

A short synthesis of racemic natural product (1) from the known compound (7) is described.A model study, using cyclohexanone as starting material, is also reported.