65488-03-1

Upstream product

• 110-53-2 1-Bromopentane 
• 100-52-7 benzaldehyde 
• 14402-93-8 dipentylzinc 
• 693-25-4 n-pentylmagnesium bromide 
• 6111-82-6 (E)-1-phenyl-1-hexene 
• 178532-48-4 (1R,2S)-1-Phenyl-2-phenylselanyl-hexan-1-ol 
• 178532-49-5 (1S,2S)-1-Phenyl-2-phenylselanyl-hexan-1-ol 
• 66-25-1 hexanal 
• 98-80-6 phenylboronic acid 
• 942-92-7 caprophenone 
• 98-86-2 acetophenone 
• 543-59-9 1-Chloropentane 
• 928-95-0 (E)-2-Hexen-1-ol 
• 821-41-0 5-Hexen-1-ol 

Relevant academic research and scientific papers

β-Silyl diorganozinc compounds - A new class of useful zinc reagents

Better synthetic efficiency is achieved in 1,4-additions in NMP:THF mixtures and in enantioselective additions to aldehydes when the diorganozinc compounds R(TMSM)Zn are used instead of R2Zn (NMP = N-methylpyrrolidone, TMSM = Me3SiCH

Multicatalytic approach to one-pot stereoselective synthesis of secondary benzylic alcohols

One-pot procedures bear the potential to rapidly build up molecular complexity without isolation and purification of consecutive intermediates. Here, we report multicatalytic protocols that convert alkenes, unsaturated aliphatic alcohols, and aryl boronic acids into secondary benzylic alcohols with high stereoselectivities (typically >95:5 er) under sequential catalysis that integrates alkene cross-metathesis, isomerization, and nucleophilic addition. Prochiral allylic alcohols can be converted to any stereoisomer of the product with high stereoselectivity (>98:2 er, >20:1 dr).

A relay catalysis strategy for enantioselective nickel-catalyzed migratory hydroarylation forming chiral α-aryl alkylboronates

Ligand-controlled reactivity plays an important role in transition-metal catalysis, enabling a vast number of efficient transformations to be discovered and developed. However, a single ligand is generally used to promote all steps of the catalytic cycle (e.g., oxidative addition, reductive elimination), a requirement that makes ligand design challenging and limits its generality, especially in relay asymmetric transformations. We hypothesized that multiple ligands with a metal center might be used to sequentially promote multiple catalytic steps, thereby combining complementary catalytic reactivities through a simple combination of simple ligands. With this relay catalysis strategy (L/L?), we report here the first highly regio- and enantioselective remote hydroarylation process. By synergistic combination of a known chain-walking ligand and a simple asymmetric cross-coupling ligand with the nickel catalyst, enantioenriched α-aryl alkylboronates could be rapidly obtained as versatile synthetic intermediates through this formal asymmetric remote C(sp3)-H arylation process.

Enantioselective α-Arylation of Primary Alcohols under Sequential One-Pot Catalysis

Secondary benzylic alcohols and diarylmethanols are common structural motifs of biologically active and medicinally relevant compounds. Here we report their enantioselective synthesis by α-arylation of primary aliphatic and benzylic alcohols under sequential catalysis integrating a Ru-catalyzed hydrogen transfer oxidation and a Ru-catalyzed nucleophilic addition. The method can be applied to various alcohols and aryl nucleophiles tolerating a range of functional groups, including secondary alcohols, ketones, alkenes, esters, NH amides, tertiary amines, aryl halides, and heterocycles.

Redox-driven deracemization of secondary alcohols by sequential ether/O2-mediated oxidation and Ru-catalyzed asymmetric reduction

The deracemization of benzylic alcohols has been achieved using a redox-driven one-pot two-step process. The racemic alcohols were oxidized by bis(methoxypropyl) ether and oxygen to give the ketone intermediates, followed by an asymmetric transfer hydrogenation with a chiral ruthenium catalyst. This compatible oxidation/reduction process gave the enantiomerically enriched alcohols with up to 95% ee values.

Method for synthesizing chiral alcohol through deracemization

The invention relates to a method for synthesizing chiral alcohol (formula I) through deracemization. The preparation method provided by the invention is one-pot asymmetric cascade reaction, and comprises the following steps: 1), with racemic alcohol (formula II) as a raw material and dipropylene glycol dimethyl ether as a solvent, reacting at 120 DEG C for 12 hours, and performing a dehydrogenation reaction to produce intermediate ketone (formula III); and 2), directly adding 2.5mol% of a chiral diamine metal ruthenium complex as a catalyst into a reaction system, with 5 equivalents of sodiumformate as a hydrogen source and a mixed solution of methanol and water as a solvent, reacting at 50 DEG C for 12 hours under the protection of nitrogen, and performing asymmetric transfer hydrogenation to obtain the chiral alcohol (formula I). The method has the advantages of environment-friendly synthesis such as a simple and mild reaction condition, step economy and atomic economy; and in addition, a substrate has a wide application range, the enantioselectivity is high, and the method has a broad application prospect in synthesis of chiral alcohol pharmaceutical intermediates and fine chemical raw materials.

Photoenzymatic Catalysis Enables Radical-Mediated Ketone Reduction in Ene-Reductases

Flavin-dependent ene-reductases (EREDs) are known to stereoselectively reduce activated alkenes, but are inactive toward carbonyls. Demonstrated here is that in the presence of photoredox catalysts, these enzymes will reduce aromatic ketones. Mechanistic experiments suggest this reaction proceeds through ketyl radical formation, a reaction pathway that is distinct from the native hydride-transfer mechanism. Furthermore, this reactivity is accessible without modification of either the enzyme or cofactors, allowing both native and non-natural mechanisms to occur simultaneously. Based on control experiments, we hypothesize that binding to the enzyme active site attenuates the reduction potential of the substrate, enabling single-electron reduction. This reactivity highlights opportunities to access new catalytic manifolds by merging photoredox catalysis with biocatalysis.

Rapid Access to Highly Functionalized Alkyl Boronates by NiH-Catalyzed Remote Hydroarylation of Boron-Containing Alkenes

The direct and selective functionalization of relatively simple and readily accessible precursors to produce highly functionalized alkyl boronates is a synthetically useful process. Herein we report a NiH-catalyzed remote hydroarylation process that can, through a synergistic combination of chain walking and subsequent cross-coupling, introduce an aryl group at the adjacent carbon atom of alkyl boronates under mild conditions. By means of a preliminary experiment with moderate enantioselectivity, it was shown that an asymmetric version could also be realized.

One-pot synthesis of chiral alcohols from alkynes by CF3SO3H/ruthenium tandem catalysis

A practical one-pot synthesis of chiral alcohols from readily available alkynes via tandem catalysis by the combination of CF3SO3H and a fluorinated chiral diamine Ru(ii) complex in aqueous CF3CH2OH is described. Very interestingly, the combination of fluorinated catalysts and solvent exhibits a positive fluorine effect on the reactivity and enantioselectivity. A range of chiral alcohols with wide functional group tolerance was obtained in high yield and excellent stereoselectivity under simple and mild conditions.

Method for direct conversion of aromatic alkyne into chiral alcohol through one-pot process

The invention relates to a method for direct conversion of aromatic alkyne into chiral alcohol through a one-pot process. The method uses cheap and easily-available alkyne I as a raw material, adoptsa two-step one-pot strategy for direct synthesis of chiral alcohol II, and comprises the following concrete steps: step 1) with fluorine-containing alcohol and water as solvents, allowing the alkyne Ito generate a hydration reaction under the catalysis of trifluoromethanesulfonic acid so as to generate an intermediate namely ketone; and step 2) directly adding a complex of monossulfonyl chiral diamine and metal ruthenium or rhodium or iridium as a catalyst into a reaction system, and with a mixture of a sodium formate aqueous solution or formic acid-triethylamine as a hydrogen source, carrying out an asymmetric transfer hydrogenation reaction so as to obtain a product II. The method provided by the invention has the following advantages: operation is simple and convenient; reaction conditions are mild; and a substrate has wide application range and high enantioselectivity. Concretely, the method provided by the invention has a general reaction formula which is described in the specification.