125847-56-5

Upstream product

• 58649-21-1 (E)-(3-chloroprop-1-en-1-yl)cyclohexane 
• 75-16-1 methylmagnesium bromide 
• 544-97-8 dimethyl zinc(II) 
• 463933-92-8 diethyl (E)-3-cyclohexyl-2-propenyl phosphate 
• 917-64-6 methyl magnesium iodide 
• 42134-55-4 (E)-3-cyclohexyl-2-propen-1-ol 
• 75-24-1 trimethylaluminum 
• 131719-68-1 1-[(E)-3-bromo-1-propenyl]cyclohexane 
• 1136238-60-2 C₁₃H₂₅O₄P 
• 131719-67-0 (E)-3-cyclohexylbut-2-en-1-ol 
• 155184-90-0 (E)-3-cyclohexylbut-2-en-1-yl methyl carbonate 
• 2043-61-0 cyclohexanecarbaldehyde 
• 4352-44-7 1-cyclohexylprop-2-en-1-ol 

Downstream Products

• 6051-13-4 2-cyclohexylpropanoic acid 

Relevant academic research and scientific papers

Improvements and Applications of the Transition Metal-Free Asymmetric Allylic Alkylation using Grignard Reagents and Magnesium Alanates

Two new N-heterocyclic carbene (NHC) ligands have been synthesized and employed in the transition metal-free asymmetric allylic alkylation (AAA) mediated by Grignard reagents and magnesium alanates. The employment of these ligands showed high yields and improved regio- and enantioselectivity in the formation of tertiary and quaternary stereocenters. Moreover, the low catalyst loading (up to 0.3 mol%) and high scalability (up to 10 mmol) of this improved methodology provide a convenient access to biologically active compounds and synthetically valuable intermediates.

Bidentate hydroxyalkyl NHC ligands for the copper-catalyzed asymmetric allylic substitution of allyl phosphates with grignard reagents

Demonstrating their potential: Bidentate alkoxy NHC ligands have been used in the copper-catalyzed asymmetric allylic alkylation of allyl phosphates with Grignard reagents (see scheme). The method provides access to tertiary and quaternary chiral centers with high regio- and enantioselectivity. The system is also applied to the synthesis of chiral E,E-dienes, a key structural motif prevalent in natural products. Copyright

Stereogenic-at-metal Zn- and Al-based N-Heterocyclic Carbene (NHC) complexes as bifunctional catalysts in Cu-free enantioselective allylic alkylations

Investigations detailed herein demonstrate the ability of chiral bidentate N-heterocyclic carbenes to promote directly - without the need for a Cu salt - site- and enantioselective C-C bond forming reactions. Within this context, catalytic allylic alkylat

High diversity on simple substrates: 1,4-dihalo-2-butenes and other difunctionalized allylic halides for copper-catalyzed SN2′ reactions

Enantioselective allylic alkylation with an organomagnesium reagent catalyzed by copper thiophene carboxylate (CuTC) was carried out on difunctionalized substrates, such as commercially available 1,4-dichloro-2- butene and 1,4-dibromo-2-butene, and on similar compounds of higher substitution pattern of the olefin for the formation of all-carbon chiral quaternary centers. The high regioselectivity obtained throughout the reactions favored good regiocontrol for the addition of phenyl Grignard reagents. Other difunctionalized substrates (allylic ethers and allylic alcohols) also underwent asymmetric SN2′ substitution.

Enantioselective copper-mediated allylic substitution with Grignard reagents employing a chiral reagent-directing leaving group

Enantioselective copper-mediated allylic substitution with Grignard reagents was achieved employing the ortho-diphenylphosphanylferrocene carboxylate (o-DPPF) system as a planar chiral reagent-directing leaving group. Careful optimization of reaction parameters resulted in excellent regioselectivities and enantioselectivies of up to 95% ee.

A readily available chiral Ag-based N-heterocyclic carbene complex for use in efficient and highly enantioselective Ru-catalyzed olefin metathesis and Cu-catalyzed allylic alkylation reactions

A new chiral bidentate N-heterocyclic carbene (NHC) ligand has been designed and synthesized. The NHC ligand bears a chiral diamine backbone and an achiral biphenol group; upon metal complexation (derived from Ag(I), Ru(II), or Cu(II)), the diamine moiety

Cu-catalyzed asymmetric allylic alkylations of aromatic and aliphatic phosphates with alkylzinc reagents. An effective method for enantioselective synthesis of tertiary and quaternary carbons

Efficient enantioselective Cu-catalyzed allylic alkylations of aromatic and aliphatic allylic phosphates bearing di- and trisubstituted olefins are disclosed. Enantioselective C-C bond forming reactions are promoted in the presence of 10 mol % readily available chiral amino acid-based ligand (5 steps, 40% overall yield synthesis) and 5 mol % (CuOTf)2·C 6H6. Reactions deliver tertiary and quaternary stereogenic carbon centers regioselectively and in 78-96% ee. Data regarding the effect of variations in ligand structure on the efficiency and enantioselectivity of the alkylation process, as well as a mechanistic working model, are presented. The suggested model involves a dual role for the chiral Cu complex: association of the Cu(I) center to the olefin is facilitated by a two-point binding between the carbonyl of the ligand's amide terminus and the P=O of the substrate.

Copper catalyzed enantioselective allylic substitution by MeMgX

Methyl Grignard undergoes highly regio (>90/10) and enantioselective (ee 91-96%) copper catalyzed allylic substitution on cinnamyl-type chlorides. CuBr (3%) and 3.3% of a chiral phosphoramidite ligand are sufficient for a complete reaction. The synthesis of a precursor of (+)-Naproxen is described. The reaction can be extended to alkyl substituted allylic chlorides (ee 72%).

Palladium-catalyzed asymmetric reduction of racemic allylic esters with formic acid: Effects of phosphine ligands on isomerization of π- allylpalladium intermediates and enantioselectivity

A new MOP ligand (lb), (R)-(+)-2-(bis(3- trifluoromethylphenyl)phosphino)-2'-methoxy-1,1'-binaphthyl, was found to be more enantioselective than other MOP ligands for the palladium-catalyzed asymmetric reduction of α,α-disubstituted allylic esters with formic acid. The reduction of DL-2-(1-naphthyl)-3-buten-2-yl benzoate gave 3-(1-naphthyl)- 1-butene of 90% ee. The higher enantioselectivity of lb is ascribed to fast syn-anti isomerization of π-allylpalladium intermediates formed by oxidative addition of allylic ester to a palladium(0) species. The rate of syn-anti isomerization was measured by the magnetization saturation transfer in 1H NMR. (C) 2000 Elsevier Science Ltd.

Tertiary phosphine compound and transition metal complex comprising the same as ligand

A tertiary phosphine compound of the formula (1): STR1 wherein R1 and R2 represent independently from each other a hydrogen atom or a methyl group, or together form --CH=CH--CH=CH--; R3 is a hydrogen atom or a cycloalkyl group having 5 to 7 carbon atoms or a lower alkyl group which may be substituted with a halogen atom, a lower alkoxy group, a lower alkoxyalkoxy group or a phenyl group; X1 is a halogen atom when both R1 and R2 are hydrogen atoms, or a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group when at least one of R1 and R2 is not a hydrogen atoms; and m is an integer of 1 to 5, which is useful as a ligand of a transition metal complex that can catalyze various reactions.