34881-29-3

Upstream product

• 62640-00-0 chlorocarbonic acid-((R)-1-methyl-heptyl ester) 
• 65-85-0 benzoic acid 
• 614-45-9 tert-Butyl peroxybenzoate 
• 111265-18-0 (S)-(+)-2-octyl phenyl sulfide 
• 6169-06-8 (S)-2-Octanol 
• 5978-70-1 (R)-Octan-2-ol 
• 111-13-7 hexyl-methyl-ketone 
• 98-88-4 benzoyl chloride 
• 36404-22-5 (R)-(-)-Oct-2-yl-N,N'-tetraaethyl-phosphorodiamid 
• 582-25-2 Potassium benzoate 
• 5978-70-1 (-)-2-octanol 
• 626-67-5 N-methylcyclohexylamine 
• 1311267-19-2 oct-2-en-2-yl benzoate 
• 6033-24-5 (R)-2-heptanol 

Downstream Products

• 5978-70-1 (R)-Octan-2-ol 

Relevant academic research and scientific papers

Enantioselective addition of dimethylzinc to aldehydes catalyzed by a chiral perhydro-1,3-benzoxazine-based amino alcohol as ligand

Dimethylzinc undergoes efficient enantioselective addition to a wide variety of aromatic and aliphatic aldehydes in the presence of a catalytic amount of a chiral perhydro-1,3-benzoxazine-based amino alcohol. Methyl carbinols are obtained in good yields and in enantiomeric excesses of 99% or more in the absence of any metal other than zinc. Georg Thieme Verlag Stuttgart · New York.

Impurity annihilation: Chromatography-free parallel Mitsunobu reactions

Mitsunobu reaction of an alcohol ROH with a carboxylic acid, phthalimide, or N-hydroxyphthalimide (NuH) using DNAD (4) and (diphenylphosphino)polystyrene (11) gave the products RNu. Ring-opening metathetic polymerization of the side product DNADH2 (3) using Cl2(Cy3P)2Ru=CHPh (13) and filtration, to remove poly(DNADH2), (diphenylphosphino)polystyrene 11, its oxide, and its adduct with excess DNAD, gave RNu (43-100%, 86-96% purity) without recourse to chromatography.

Mechanism-Based Enantiodivergence in Manganese Reduction Catalysis: A Chiral Pincer Complex for the Highly Enantioselective Hydroboration of Ketones

A manganese alkyl complex containing a chiral bis(oxazolinyl-methylidene)isoindoline pincer ligand is a precatalyst for a catalytic system of unprecedented activity and selectivity in the enantioselective hydroboration of ketones, thus producing preparatively useful chiral alcohols in excellent yields with up to greater than 99 % ee. It is applicable for both aryl alkyl and dialkyl ketone reduction under mild reaction conditions (TOF >450 h?1 at ?40 °C). The earth-abundant base-metal catalyst operates at very low catalyst loadings (as low as 0.1 mol %) and with a high level of functional-group tolerance. There is evidence for the existence of two distinct mechanistic pathways for manganese-catalyzed hydride transfer and their role for enantiocontrol in the selectivity-determining step is presented.

Broad Scope Synthesis of Ester Precursors of Nonfunctionalized Chiral Alcohols Based on the Asymmetric Hydrogenation of α,β-Dialkyl-, α,β-Diaryl-, and α-Alkyl-β-aryl-vinyl Esters

The catalytic asymmetric hydrogenation of trisubstituted enol esters using Rh catalysts bearing chiral phosphine-phosphite ligands (P-OP) has been studied. Substrates covered comprise α,β-dialkyl, α-alkyl-β-aryl, and α,β-diarylvinyl esters, the corresponding hydrogenation products being suitable precursors to prepare synthetically relevant chiral nonfunctionalized alcohols. A comparison of reactivity indicates that it decreases in the order: α,β-dialkyl > α-alkyl-β-aryl > α,β-diaryl. Based on the highly modular structure of P-OP ligands employed, catalyst screening identified highly enantioselective catalysts for α,β-dialkyl (95-99% ee) and nearly all of α-alkyl-β-aryl substrates (92-98% ee), with the exception of α-cyclohexyl-β-phenylvinyl acetate which exhibited a low enantioselectivity (47% ee). Finally, α,β-diarylvinyl substrates showed somewhat lower enantioselectivities (79-92% ee). In addition, some of the catalysts provided a high enantioselectivity in the hydrogenation of E/Z mixtures (ca. Z/E = 75:25) of α,β-dialkylvinyl substrates, while a dramatic decrease on enantioselectivity was observed in the case of α-methyl-β-anisylvinyl acetate (Z/E = 58:42). Complementary deuteration reactions are in accord with a highly enantioselective hydrogenation for both olefin isomers in the case of α,β-dialkylvinyl esters. In contrast, deuteration shows a complex behavior for α-methyl-β-anisylvinyl acetate derived from the participation of the E isomer in the reaction.

Majority-Rules-Type Helical Poly(quinoxaline-2,3-diyl)s as Highly Efficient Chirality-Amplification Systems for Asymmetric Catalysis

A highly efficient majority-rules effect of poly(quinoxaline-2,3-diyl)s (PQXs) bearing 2-butoxymethyl chiral side chains at the 6- and 7-positions was established and attributed to large ΔGh values (0.22-0.41 kJmol-1), which are defined as the energy difference between P- and M-helical conformations per chiral unit. A PQX copolymer prepared from a monomer derived from (R)-2-octanol (23% ee) and a monomer bearing a PPh2 group adopted a single-handed helical structure (>99%) and could be used as a highly enantioselective chiral ligand in palladium-catalyzed asymmetric reactions (products formed with up to 94% ee), in which the enantioselectivity could be switched by solvent-dependent inversion of the helical PQX backbone. Bowing to the majority: Poly(quinoxaline-2,3-diyl) containing PPh2 groups and chiral side chains derived from (R)-2-octanol with 23% ee exhibited a single-handed-helical conformation and served as a highly enantioselective chiral ligand in palladium-catalyzed reactions (see scheme; se=screw-sense excess). The chirality of the polymer could be switched by a solvent effect to enable the synthesis of the enantiomeric products.

Development of a redox-free Mitsunobu reaction exploiting phosphine oxides as precursors to dioxyphosphoranes

The development of the first redox-free protocol for the Mitsunobu reaction is described. This has been achieved by exploiting triphenylphosphine oxide-the unwanted by-product in the conventional Mitsunobu reaction-as the precursor to the active P(v) coupling reagent. Multinuclear NMR studies are consistent with hydroxyl activation via an alkoxyphosphonium salt.

Regio- and stereochemistry of Na-mediated reductive cleavage of alkyl aryl ethers

We have investigated the regio-and stereochemistry of the reductive dealkoxylation of alkyl aryl ethers. Chiral non-racemic secondary alcohols were converted into the corresponding m-terphenyl or 2-biphenyl ethers either via inversion of configuration under Mitsunobu reaction conditions or with retention of configuration under SNAr conditions. The successive cleavage of the aromatic C-O bond occurred in the presence of a stoichiometric amount of Na metal in dry tetrahydrofuran at rt with retention of configuration, thus highlighting that the overall inversion or retention of configuration for the whole two-step procedure is dictated by the stereochemistry of the first synthetic step.

Asymmetric hydrogenation of 1-alkyl and 1-aryl vinyl benzoates: A broad scope procedure for the highly enantioselective synthesis of 1-substituted ethyl benzoates

The enantioselective hydrogenation of enol esters of formula CH2=C(OBz)R with rhodium catalysts based on phosphine-phosphite ligands (P-OP) has been studied. The reaction has a broad scope, and it is suitable for the preparation of products pos

Highly enantioselective Rh-catalysed hydrogenation of 1-alkyl vinyl esters using phosphine-phosphoramidite ligands

MatPhos, a good mate for hard tasks: The asymmetric hydrogenation of 1-alkyl vinyl esters, thwarted so far by mediocre ee values and low activities, can now be achieved with MatPhos/Rh catalysts with ee values of 96-99 % for a variety of substrates at low catalyst loadings (0.1-1 mol %) and under mild conditions (5-20 bar H2, room temperature). After hydrolysis, the corresponding chiral secondary alkyl alcohols can be obtained in high enantiopurities providing a general and practical route to this important product class. Copyright

Highly enantioselective hydrogenation of 1-alkylvinyl benzoates: A simple, nonenzymatic access to chiral 2-alkanols

Going chiral! Highly enantioselective catalytic hydrogenations of enol esters 1 by using a Rh catalyst bearing a P?￡?OP ligand are described (see scheme; NBD=norbornadiene). The catalytic system has a broad scope and allows the preparation of a wide range of chiral esters 2 bearing diverse alkyls or a benzyl group with high enantioselectivities. These esters can easily be converted in highly enantioenriched 2-alkanols. Copyright