40028-00-0

Upstream product

• 115510-91-3 1-(thien-2-yl)ethanol 
• 100-51-6 benzyl alcohol 
• 88-15-3 2-Acetylthiophene 
• 100-52-7 benzaldehyde 

Downstream Products

• 532984-19-3 (3R)-4-(4-toluenesulfonyl)thiomorpholine-3-carboxylic acid [3-phenyl-1-(thiophen-2-yl)]-propyl ester 

Relevant academic research and scientific papers

Reaction condition controlled nickel(ii)-catalyzed C-C cross-coupling of alcohols

The challenge in the C-C cross-coupling of secondary and primary alcohols using acceptorless dehydrogenation coupling (ADC) is the difficulty in accurately controlling product selectivities. Herein, we report a controlled approach to a diverse range of β-alkylated secondary alcohols, α-alkylated ketones and α,β-unsaturated ketones using the ADC methodology employing a Ni(ii) 4,6-dimethylpyrimidine-2-thiolate cluster catalyst under different reaction conditions. This catalyst could tolerate a wide range of substrates and exhibited a high activity for the annulation reaction of secondary alcohols with 2-aminobenzyl alcohols to yield quinolines. This work is an example of precise chemoselectivity control by careful choice of reaction conditions.

Electronically tuneable orthometalated RuII–NHC complexes as efficient catalysts for C–C and C–N bond formations via borrowing hydrogen strategy

The catalytic activities of a series of simple and electronically tuneable cyclometalated RuII–NHC complexes (2a–d) were explored in various C–C/N bond formations following the borrowing hydrogen process. Slight modifications in the ligand backbone were noted to tune the activities of these complexes. Among them, the complex 2d featuring a 1,2,4-triazolylidene donor with a 4-NO2–phenyl substituent displayed the highest activity for the coupling of diverse secondary and primary alcohols with a low catalyst loading of 0.01 mol% and a sub-stoichiometric amount of inexpensive KOH base. The efficacy of this simple system was further showcased in the challenging one-pot unsymmetrical double alkylation of secondary alcohols using different primary alcohols. Moreover, the complex 2d also effectively catalyses the selective mono-N-methylation of various aromatic and aliphatic primary amines using methanol to deliver a range of N-methyl amines. Mechanistically, the β-alkylation reaction follows a borrowing hydrogen pathway which was established by the deuterium labelling experiment in combination with various control experiments. Intriguingly, in situ1H NMR and ESI-MS analyses evidently suggested the involvement of a Ru–H species in the catalytic cycle and further, the kinetic studies revealed a first order dependence of the reaction rate on the catalyst as well as the alcohol concentrations.

Pincer-Nickel Catalyzed Selective Guerbet-Type Reactions

We report here the synthesis and characterization of a series of NNN pincer-nickel complexes of the type (R2NNN)NiCl2(CH3CN) (R = iPr, tBu, Cy, Ph, and p-F-C6H4) based on bis(imino)pyridine ligands. In solution, these complexes are found to be equilibrium mixtures containing one and two pincer ligands, respectively. While the crystal structure of the former was reported by us recently for R = iPr, we report the crystal structure of the latter in this study for R = p-F-C6H4. The considered NNN pincer-Ni complexes have been successfully employed to accomplish the catalytic β-alkylation of several secondary alcohols with a variety of benzyl alcohols at 140 °C with high yields and unprecedented turnovers. A maximum of 92% yield of the β-alkylated product at 18 ?400 TON was obtained in the reaction of benzyl alcohol with 1-(4-(trifluoromethyl)phenyl)ethane-1-ol in the presence of 0.005 mol % of (Ph2NNN)NiCl2(CH3CN) and 5 mol % of NaOtBu at 140 °C after 24 h. The reaction exhibits zero-order dependence of rate on catalyst concentration and first-order dependence on the concentration of base, benzyl alcohol, and 1-phenyl ethanol which points to the base-mediated aldol condensation as the rate-determining step. Most of the intermediates involved in catalysis have been identified by HRMS. To the best of our knowledge, this is the first report on a pincer-Ni catalyzed β-alkylation of alcohols and, hitherto, such unprecedented turnovers have not been reported with a homogeneous molecular nickel-based catalyst.

Cobalt-Catalyzed Alkylation of Secondary Alcohols with Primary Alcohols via Borrowing Hydrogen/Hydrogen Autotransfer

Alcohols are promising sustainable starting materials because they can be obtained from abundant and indigestible biomass. The substitution of expensive noble metals in catalysis by earth abundant 3d metals, such as Mn, Fe, or Co, (nonprecious or base metals) is a related key concept with respect to sustainability. Here, we report on the first cobalt-catalyzed alkylation of secondary alcohols with primary alcohols. Easy-to-synthesize and easy-to-activate PN5P-pincer-ligand-stabilized Co complexes developed in our laboratory mediate the reaction most efficiently. The catalysis is applicable to a broad substrate scope and proceeds under relatively mild conditions. We have even demonstrated the coupling of a variety of purely aliphatic alcohols with a base or nonprecious metal catalyst. Mechanistic studies indicate that the reaction follows the borrowing hydrogen or hydrogen autotransfer concept.

Catalyst-free dehydrative α-alkylation of ketones with alcohols: Green and selective autocatalyzed synthesis of alcohols and ketones

Direct dehydrative α-alkylation reactions of ketones with alcohols are now realized under simple, practical, and green conditions without using external catalysts. These catalyst-free autocatalyzed alkylation methods can efficiently afford useful alkylated ketone or alcohol products in a one-pot manner and on a large scale by Ci￡C bond formation of the in situ generated intermediates with subsequent controllable and selective Meerwein-Pondorf-Verley-Oppenauer-type redox processes. Plain and simple: The title reaction has been realized under simple and practical conditions without using external catalysts, and can afford alkylated ketone or alcohol products in a one-pot manner and on a large scale. The reaction proceeds by Ci￡C bond formation of the in situ generated intermediates with subsequent controllable and selective Meerwein-Pondorf-Verley-Oppenauer-type redox processes. Copyright

Carbon-carbon bond formation between secondary alcohols and aldehydes under ruthenium-catalyzed redox shuttle

Secondary alcohols are coupled with aldehydes in dioxane in the presence of a catalytic amount of a ruthenium catalyst along with KOH to give coupled ketones or coupled secondary alcohols depending on the molar ratio of secondary alcohols to aldehydes and the presence (or absence) of a sacrificial hydrogen acceptor. Copyright