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Upstream product

• 22627-45-8 3-(3-butenyl)cyclohex-2-en-1-one 
• 1193-18-6 3-methylcyclohexen-2-one 
• 7103-09-5 4-but-1-enylmagnesium bromide 
• 5323-87-5 3-Ethoxycyclohex-2-en-1-one 
• 75-24-1 trimethylaluminum 

Downstream Products

• 121363-32-4 2-((S)-3-But-3-enyl-3-methyl-cyclohexylidene)-[1,3]dithiane 
• 121363-37-9 (S)-3-But-3-enyl-3-methyl-cyclohexanecarboxylic acid methyl ester 
• 121363-33-5 (S)-3-But-3-enyl-3-methyl-cyclohexanecarboxylic acid 

Relevant academic research and scientific papers

Formation of quaternary chiral centers by N-Heterocyclic carbene-CuCatalyzed asymmetric conjugate addition reactions with grignard reagents on trisubstituted cyclic enones

The copper-catalyzed conjugate addition of Grignard reagents to 3-substituted cyclic enones allows the formation of all-carbon chiral quaternary centers. We demonstrate in this article that N-heterocyclic carbenes act as efficient chiral ligands for this transformation. High enantioselectivities (up to 96% ee) could be obtained for a variety of substrates.

C2 symmetric chiral NHC ligand for asymmetric quaternary carbon constructing copper-catalyzed conjugate addition of Grignard reagents to 3-substituted cyclohexenones

(Chemical Equation Presented) The asymmetric construction of quaternary carbon centers by conjugate addition of Grignard reagents to 3-methyl- and 3-ethylcyclohexenones was realized in a maximum enantioselectivity of 80% by using a C2 symmetric chiral N-heterocyclic carbene (NHC)-copper catalyst, generated from (4S,5S)-1,3-bis(2-methoxyphenyl)-4,5-diphenyl-4,5- dihydro-1H-imidazol-3-ium tetrafluoroborate and copper(II) triflate. The stereostructures of the NHC-Au complexes were analyzed by X-ray crystallography, which rationalized the good stereocontrolling ability of N-aryl NHCs.

Copper-catalyzed asymmetric conjugate addition of trialkylaluminium reagents to trisubstituted enones: Construction of chiral quaternary centers

Me3Al, Et1Al, and vinylalane species undergo enantioselective conjugate addition to a wide range of 2- or 3-substituted enones (cyclopent-2enones, cyclohex-2-enones, 3-methyl cyclohept-2-enone) in the presence of catalytic amount of copper salt (copper thiophene carboxylate, [Cu(CH3-CN)4]BF4 or [CuOTf]2· C6H6) and tropos-phosphoramidite-based ligand. Thus, chiral quaternary centers can be built, with up to 98% ee after rigorous optimization of experimental conditions. It was shown that the main important parameter was the order of the introduction of the reagents. Then, the generated enantioenriched aluminium enolates and the chiral conjugate adducts were functionalized and used for subsequent reactions.

Copper-catalyzed asymmetric conjugate addition of Grignard reagents to trisubstituted enones. Construction of all-carbon quaternary chiral centers

The copper-catalyzed asymmetric conjugate addition of Grignard reagents to trisubstituted cyclic enones affords enantioenriched all-carbon quaternary centers with up to 96% ee. The chiral ligand is a diaminocarbene, directly generated in situ. The combination of Grignard reagent and diaminocarbene is unprecedented in conjugate addition, and the additon of the phenyl group, on such enones, cannot be done by other conjugate addition methods. Copyright

Enantioselective copper-catalyzed conjugate addition to trisubstituted cyclohexenones: Construction of stereogenic quaternary centers

Trimethyl- and triethylaluminum undergo enantioselective conjugate addition to 3-and 2-substituted cyclohexenones in the presence of catalytic amounts of a Cu salt and a phosphoramidite ligand L* (see scheme). Thus, chiral quaternary centers can be built with up to 96.6% ee. Functionalized enones lead to bicyclic structures by a subsequent aldol reaction.

PREPARATION OF BRIDGED BICYCLOALKANES VIA INTRAMOLECULAR CYCLOADDITIONS OF KETENES. A SHORT TOTAL SYNTHESIS OF (+/-)-CLOVENE.

The preparation of a bridged bicycloalkane via an intramolecular ketene-olefin cycloaddition reaction in the context of a total synthesis of clovene is described.