73232-03-8

Upstream product

• 1474-78-8 triethyl phosphonoformate 
• 823-76-7 Cyclohexyl methyl ketone 
• 28811-84-9 ethyl 3-hydroxy-3-cyclohexylbutyrate 
• 867-13-0 diethoxyphosphoryl-acetic acid ethyl ester 
• 4341-76-8 Ethyl 2-butynoate 
• 931-51-1 cyclohexylmagnesiumchloride 
• 931-48-6 2-cyclohexylacetylene 
• 75-24-1 trimethylaluminum 
• 541-41-3 chloroformic acid ethyl ester 

Downstream Products

• 1332864-78-4 (E)-(tert-butyl) 1-(3-cyclohexylbut-2-enyl)hydrazinecarboxylate 
• 1332865-05-0 tert-butyl 2-(2-cyclohexylbut-3-en-2-yl)diazenecarboxylate 
• 28811-80-5 ethyl (S)-3-cyclohexylbutanoate 
• 66938-07-6 (3R)-3-cyclohexylbutanal 
• 110065-44-6 (3S)-3-cyclohexylbutanal 

Relevant academic research and scientific papers

Cobalt-Catalyzed Asymmetric 1,4-Reduction of β,β-Dialkyl α,β-Unsaturated Esters with PMHS

A cobalt-catalyzed asymmetric reduction of β,β-dialkyl α,β-unsaturated esters with polymethylhydrosiloxane (PMHS) was reported to deliver the corresponding esters containing a chiral trialkyl carbon center at β-position with up to 97 % yield and 98 % ee. The chiral tridentate ligand oxazoline iminopyridine (OIP) could perform well for the asymmetric reduction instead of chiral bidentate ligands. This operationally simple protocol shows a broad scope of substrates using one equivalent of readily available PMHS as a cheap and easy-to-handle reductive reagent.

An entry to non-racemic β-tertiary-β-amino alcohols, building blocks for the synthesis of aziridine, piperazine, and morpholine scaffolds

A method for the preparation of enantiopure β-tert-amino alcohols bearing a tetrasubstituted C-stereocenter, as well as their conversion into selected medicinally privileged heterocyclic systems (morpholines, aziridines, piperazines) is reported. These co

Enantioselective epoxidation of β,β-disubstituted enamides with a manganese catalyst and aqueous hydrogen peroxide

Enantioselective epoxidation of β,β-disubstituted enamides with aqueous hydrogen peroxide and a novel manganese catalyst is described. Epoxidation is stereospecific and proceeds fast under mild conditions. Amides are disclosed as key functional groups to enable high enantioselectivity.

Catalytic hydrogenation of α,β-unsaturated carboxylic acid derivatives using copper(i)/N-heterocyclic carbene complexes

A simple and air-stable copper(i)/N-heterocyclic carbene complex enables the catalytic hydrogenation of enoates and enamides, hitherto unreactive substrates employing homogeneous copper catalysis and H2 as a terminal reducing agent. This atom economic transformation replaces commonly employed hydrosilanes and can also be carried out in an asymmetric fashion.

Iminium Catalysis inside a Self-Assembled Supramolecular Capsule: Scope and Mechanistic Studies

Although iminium catalysis has become an important tool in organic chemistry, its combination with supramolecular host systems has remained largely unexplored. We report the detailed investigations into the first example of iminium catalysis inside a supramolecular host. In the case of 1,4-reductions of α,β-unsaturated aldehydes, catalytic amounts of host are able to increase the enantiomeric excess of the products formed. Several control experiments were performed and provided strong evidence that the modulation of enantiomeric excess of the reaction product indeed stems from a reaction on the inside of the capsule. The origin of the increased enantioselectivity in the capsule was investigated. Furthermore, the substrate and nucleophile scope were studied. Kinetic investigations as well as the kinetic isotope effect measured confirmed that the hydride delivery to the substrate is the rate-determining step inside the capsule. The exploration of benzothiazolidines as alternative hydride sources revealed an unexpected substitution effect of the hydride source itself. The results presented confirm that the noncovalent combination of supramolecular hosts with iminium catalysis is opening up new exciting possibilities to increase enantioselectivity in challenging reactions.

Iminium Catalysis inside a Self-Assembled Supramolecular Capsule: Modulation of Enantiomeric Excess

The noncovalent combination of a supramolecular host with iminium organocatalysis is described. Due to cation–π interactions the reactive iminium species is held inside the host and reacts in this confined environment. The products formed differ up to 92 % ee from the control experiments without added host. A model rationalizing the observed difference is presented.

Enantioselective Hydrogenation of β,β-Disubstituted Unsaturated Carboxylic Acids under Base-Free Conditions

An additive-free enantioselective hydrogenation of β,β-disubstituted unsaturated carboxylic acids catalyzed by the Rh-(R,R)-f-spiroPhos complex has been developed. Under mild conditions, a wide scope of β,β-disubstituted unsaturated carboxylic acids were hydrogenated to the corresponding chiral carboxylic acids with excellent enantioselectivities (up to 99.3% ee). This methodology was also successfully applied to the synthesis of the pharmaceutical molecule indatraline.

Highly efficient Rh-catalyzed asymmetric hydrogenation of α,β-unsaturated nitriles

A highly efficient enantioselective hydrogenation of α,β-unsaturated nitriles catalyzed by Rh-(R,R)-f-spiroPhos complex has been developed. With Rh-(R,R)-f-spiroPhos catalyst and under mild conditions, a wide range of α,β-unsaturated nitriles including the (E)- and (Z)-isomers of 3-alkyl-3-aryl, 3,3-diaryl, and 3,3-dialkyl α,β-unsaturated nitriles were hydrogenated to the corresponding chiral nitriles with excellent enantioselectivities (up to 99.9% ee) and high turnover numbers (TON up to 10,000).

Asymmetric construction of quaternary stereogenic centers via auxiliary-based SN2′ reactions: A case of 1,7-relative stereogenesis

The stereoselective construction of quaternary stereogenic centers is described that employs an allylic substitution through the intermediacy of a chiral carbamate leaving group. Five carbamates with two substituents at the allylic terminus combined with

Iridium-catalyzed asymmetric hydrogenation of 3,3-disubstituted allylic alcohols in ethereal solvents

Ir-phosphinomethyl-oxazoline complexes have been identified as efficient, highly enantioselective catalysts for the asymmetric hydrogenation of 3,3-disubstituted allylic alcohols and related homoallylic alcohols. In contrast to other N,P ligand complexes, which require weakly coordinating solvents, such as dichloromethane, these catalysts perform well in more ecofriendly THF or 2-MeTHF. Their synthetic potential was demonstrated with the formal total synthesis of four bisabolane sesquiterpenes. Particularly high enantioselectivity values in the asymmetric hydrogenation of 3,3-disubstituted allylic alcohols and related homoallylic alcohols have been achieved with Ir-phosphinomethyloxazoline catalysts. In contrast to other N,P-ligand complexes, which require weakly coordinating solvents, such as CH 2Cl2, these catalysts perform well in more ecofriendly THF or 2-MeTHF (see scheme; CODa =a 1,5-cyclooctadiene). Copyright