61925-49-3

Upstream product

• 111-71-7 heptanal 
• 557-20-0 diethylzinc 
• 108-05-4 vinyl acetate 
• 185019-15-2 nonan-3-ol 
• 925-78-0 3-nonanone 
• 66-25-1 hexanal 
• 124-13-0 Octanal 

Downstream Products

• 179066-15-0 4-Benzyloxy-3-fluoro-benzoic acid (R)-1-ethyl-heptyl ester 
• 925-78-0 3-nonanone 
• 179066-16-1 3-Fluoro-4-hydroxy-benzoic acid (R)-1-ethyl-heptyl ester 
• 61925-50-6 (R)-3-nonanol 
• 139199-72-7 C₁₉H₂₇F₃O₃ 

Relevant academic research and scientific papers

Chiral 2-(2-hydroxyaryl)alcohols (HAROLs) with a 1,4-diol scaffold as a new family of ligands and organocatalysts

Efficient and modular syntheses of chiral 2-(2-hydroxyaryl)alcohols (HAROLs), novel 1,4-diols carrying one phenolic and one alcohol hydroxyl group, have been developed which led to generation of a small library of structurally diverse HAROLs in enantiomerically pure form. Of the different HAROLs examined, a HAROL based on the indan backbone exhibited the highest activity and enantioselectivity in the 1,2-addition of certain organometallic compounds to aldehydes in the presence of Ti(OiPr)4 (up to 97% y, 88% ee) and performed as a hydrogen-bond donor organocatalyst in the Morita-Baylis-Hillman reaction, promoted by trialkylphosphines.

Mechanistic implications of the enantioselective addition of alkylzinc reagents to aldehydes catalyzed by nickel complexes with α-amino amide ligands

The enantioselective alkylation of aldehydes catalysed by nickel(ii)-complexes derived from α-amino amides was studied by means of density functional theory (DFT) and ONIOM (B3LYP:UFF) calculations. A mechanism was proposed in order to investigate the origin of enantioselectivity. The chirality-determining step for the alkylation was the formation of the intermediate complexes with the involvement of a 5/4/4-fused tricyclic transition state. The predominant products predicted theoretically were of (S)-configuration, in good agreement with experimental observations. The scope of the reaction was examined and high yields and enantioselectivities were observed for the enantioselective addition of Et2Zn and Me2Zn to aromatic and aliphatic aldehydes.

Novel C2-symmetric chiral O,N,N,O-tetradentate 2,2-bipyridyldiolpropane ligands: Synthesis and application in asymmetric diethylzinc addition to aldehydes

First synthesis of C2-symmetric chiral O,N,N,O-tetradentate 2,2-bipyridyldiolpropane ligands is described. The Mukaiyama-Michael reaction was applied as an important reaction for the synthesis of 2,2-bipyridylpropane 9. Among the ligands synthesized, ligand 11 exhibits excellent chiral induction (up to 97% ee) in diethylzinc addition to various aldehydes. The use of additional Lewis acid such as Ti(OiPr)4 in diethylzinc addition reaction is not required for the present catalytic system.

The synthesis of chiral amino diol tridentate ligands and their enantioselective induction during the addition of diethylzinc to aldehydes

A series of C2-symmetric chiral amino diol tridentate ligands 3a-g were prepared from achiral bulky organolithiums, achiral bulky primary amines, and optically active epichlorohydrin (ECH). The prepared C 2-symmetric chiral amino diol tridentate ligands were capable of inducing enantioselectivity in the model reaction of aromatic and aliphatic aldehydes with diethylzinc with an ee of up to 96%. The enantioselectivity can be modulated by adjusting the steric hindrance of the achiral reagents employed in the synthesis of the chiral ligand. The configuration of the addition product depended on the configuration of the amino diol ligands, which can be simply controlled as desired by using the ECH with the desired configuration during the preparation of the ligand.

C2 symmetrical nickel complexes derived from α-amino amides as efficient catalysts for the enantioselective addition of dialkylzinc reagents to aldehydes

A series of C2 symmetrical 1:2 Ni:L complexes derived from α-amino amides were studied for the enantioselective addition of dialkylzinc reagents to aldehydes. Different structural elements on the ligands seem to play an important role in determining the observed enantioselectivity. Through optimization of structure and reaction conditions, the best ligand provided secondary alcohols in excellent yields (up to 98%) and enantioselectivity of up to 99% ee for (R)-enantiomer. A transition state model has been proposed to explain the observed enantioselectivities based on computational calculations at the DFT level. Very interestingly, calculations suggest a coordination model of the aldehyde to the metal complex through association of a lone pair of the carbonyl oxygen to the hydrogen atom of an amino group.

Synthesis of chiral pyridylphenols for the enantioselective addition of diethylzinc to aldehydes

Chiral 8-substituted 2-(8,10,10-trimethyl-6-aza-tricyclo[7.1.1.0 2,7]undeca-2(7),3,5-trien-5-yl)-phenols were prepared from a high enantiopurity (>97% ee) of (1R)-(+)-α-pinene, and assessed in the enantioselective addition of diethylzinc to substituted benzaldehydes, giving the (S)-alcohols with enantiomeric excess ranging from 33% to 89%. Interestingly, in all cases, except for those of ortho-chlorobenzaldehyde, ortho- and para-methoxybenzaldehydes, the ee was >71%. The plot of the Hammett substitution constants vs. enantiomeric excess of the diethylzinc addition to either the ortho- or para-substituted benzaldehydes shows a linear correlation.

Highly enantioselective addition of diethylzinc to aldehydes catalyzed by novel chiral tert-amino alcohols

A series of novel chiral tert-amino alcohols 4a-h derived from enantiomerically pure phenylalanine were synthesized efficiently and used as chiral ligands in the catalytic enantioselective ethylation of aldehydes with diethylzinc (diethylzinc-to-aldehyde addition). The use of 10 mol % of the amino alcohols led to the corresponding sec-alcohols with excellent enantioselectivities (up to 100% ee) and high yields.

The synthesis of new oxazoline-containing bifunctional catalysts and their application in the addition of diethylzinc to aldehydes

The straightforward preparation of new modular oxazoline-containing bifunctional catalysts is reported employing a microwave-assisted Buchwald-Hartwig aryl amination as the key step. Covalent attachment of 2-(o-aminophenyl)oxazolines and pyridine derivati

One-way biohydrogen transfer for oxidation of sec-alcohols

(Chemical Equation Presented) Quasi-irreversible oxidation of sec-alcohols was achieved via biocatalytic hydrogen transfer reactions using alcohol dehydrogenases employing selected ketones as hydrogen acceptors, which can only be reduced but not oxidized. Thus, only 1 equiv of oxidant was required instead of a large excess. For the oxidation of both isomers of methylcarbinols a single nonstereoselective short-chain dehydrogenase/reductase from Sphingobium yanoikuyae was identified and overexpressed in E. coli.

Structural optimization of enantiopure 2-cyclialkylamino-2-aryl-1,1- diphenylethanols as catalytic ligands for enantioselective additions to aldehydes

(Chemical Equation Presented) The structural optimization of a family of modular, enantiopure β-amino alcohol ligands with a common 2-amino-2-aryl-1,1-diphenylethanol skeleton, whose stereogenicity was introduced through the Jacobsen epoxidation of 1,1-diphenyl-2-arylethylenes, has led to the identification of a small set of optimal catalysts with enhanced activity and enantioselectivity in the addition of alkylzinc and arylzinc reagents to aldehydes. Criteria for the discrimination between apparently analogous, highly enantioselective ligands are proposed.