42969-65-3

Usage

Uses

Used in Pharmaceutical Industry:
(R)-(+)-3-BUTYN-2-OL is used as a starting material for the multi-step synthesis of (R)-benzyl 4-hydroxyl-2-pentynoate, which is a key intermediate in the development of pharmaceutical compounds. Its chiral nature and unique structural features make it a valuable component in the synthesis of various drugs, particularly those targeting specific biological receptors.
Used in Chemical Synthesis:
(R)-(+)-3-BUTYN-2-OL is used as a versatile building block in the synthesis of various organic compounds due to its triple bond and hydroxyl group. These functional groups can be further modified or reacted with other molecules to create a wide range of products, including specialty chemicals, agrochemicals, and advanced materials.
Used in Research and Development:
(R)-(+)-3-BUTYN-2-OL is also utilized in research and development for the exploration of new chemical reactions and the development of innovative synthetic methods. Its unique structural features make it an interesting candidate for studying reaction mechanisms and developing new catalytic processes.

Upstream product

• 5930-98-3 4-trimethylsilyl-3-butyn-2-one 
• 42969-62-0 (+/-)-but-3'-yn-2'-yl hydrogen phthalate 
• 128241-50-9 (2R,3E)-4-iodobut-3-en-2-ol 
• 1423-60-5 methyl ethynyl ketone 
• 114351-86-9 (R)-3-butyn-2-ol hydrogen phthalate (R)-α-methylbenzylammonium salt 
• 29333-27-5 but-3-yn-2-yl benzoate 
• 2028-63-9 but-3-yn-2-ol 
• 16169-82-7 (+/-)-3-acetyloxy-1-butyne 
• 108-05-4 vinyl acetate 
• 901126-37-2 (S)-4-(triisopropylsilyl)but-3-yn-2-ol 
• 1440569-85-6 C₂₀H₂₄OSi 
• 844641-16-3 (S)-threonyl-(S)-phenylglycine 
• 117924-32-0 (R)-O-TMS-butynol 
• 129571-78-4 (R)-4-trimethylsilyl-3-butyn-2-yl acetate 

Downstream Products

• 5876-76-6 (R)-4-phenylbut-3-yn-2-ol 
• 33715-08-1 (R)-buta-1,2-dien-1-yl diphenyl phosphine oxide 
• 33715-08-1 (S)-buta-1,2-dien-1-yl diphenyl phosphine oxide 
• 1067324-45-1 (S)-3-hydroxy-2-iodobut-1(E)-enyl diphenyl phosphine oxide 
• 1067324-43-9 (R)-3-hydroxy-2-iodobut-1(E)-enyl diphenyl phosphine oxide 
• 1201839-36-2 1,3,5,7-tetrakis(4-(4-(2-(R)-hydroxyethyl)-1,2,3-triazol-1-yl)phenyl)adamantane 
• 1385765-55-8 N¹-((R)-1-(4-fluorophenyl)ethyl)-N³-((2S,3S)-3-hydroxy-4-(4-((R)-1-hydroxy ethyl)-1H-1,2,3-triazol-1-yl)-1-phenylbutan-2-yl)-5-(N-methylmethylsulfonamido)isophthalamide 
• 4070-90-0 N-methyl-N-(1-methyl-prop-2-inyl)-amine 
• 1616623-24-5 (R)-4-(3-hydroxybut-1-yn-1-yl)benzonitrile 
• 3113-93-7 Phthalic acid mono-(1-methyl-prop-2-ynyl) ester 
• 477288-58-7 (R)-((but-3-yn-2-yloxy)methyl)benzene 
• 160156-04-7 (R)-3,3,3-Trifluoro-2-methoxy-2-phenyl-propionic acid (R)-1-methyl-prop-2-ynyl ester 

Relevant academic research and scientific papers

Discovery and Redesign of a Family VIII Carboxylesterase with High (S)-Selectivity toward Chiral sec-Alcohols

Highly enantioselective lipase has been widely utilized in the preparation of versatile enantiopure chiral sec-alcohols through kinetic or dynamic kinetic resolution. Lipase is intrinsically (R)-selective, and it is difficult to obtain (S)-selective lipase. Recent crystal structures of a family VIII carboxylesterase have revealed that the spatial array of its catalytic triad is the mirror image of that of lipase but with a catalytic triad that is distinct from lipase. We, therefore, hypothesized that the family VIII carboxylesterase may exhibit (S)-enantioselectivity toward sec-alcohols similar to (S)-selective serine protease, whose catalytic triad is also spatially arrayed as its mirror image. In this study, a homologous enzyme (carboxylesterase from Proteobacteria bacterium SG_bin9, PBE) of a known family VIII carboxylesterase (pdb code: 4IVK) was prepared, which showed not only moderate (S)-selectivity toward sec-alcohols such as 3-butyn-2-ol and 1-phenylethyl alcohol but also (R)-selectivity toward particular sec-alcohols among the substrates explored. Furthermore, the (S)-selectivity of PBE has been significantly improved by rational redesign based on molecular modeling. Molecular modeling identified a binding pocket composed of Ser381, Ala383, and Arg408 for the methyl substituent of (R)-1-phenylethyl acetate and suggested that larger residues may increase the enantioselectivity by interfering with the binding of the slow-reacting enantiomer. As predicted, substituting Ser381with larger residues (Phe, Tyr, and Trp) significantly improved the (S)-selectivity of PBE toward all sec-alcohols explored, even the substrates toward which the wild-type PBE exhibits (R)-selectivity. For instance, the enantioselectivity toward 3-butyn-2-ol and 1-phenylethyl alcohol was improved from E = 5.5 and 36.1 to E = 2001 and 882, respectively, by single mutagenesis (S381F).

Enantioselective oxidation of secondary alcohols by the flavoprotein alcohol oxidase from Phanerochaete chrysosporium

The enantioselective oxidation of secondary alcohols represents a valuable approach for the synthesis of optically pure compounds. Flavoprotein oxidases can catalyse such selective transformations by merely using oxygen as electron acceptor. While many flavoprotein oxidases preferably act on primary alcohols, the FAD-containing alcohol oxidase from Phanerochaete chrysosporium was found to be able to perform kinetic resolutions of several secondary alcohols. By selective oxidation of the (S)-alcohols, the (R)-alcohols were obtained in high enantiopurity. In silico docking studies were carried out in order to substantiate the observed (S)-selectivity. Several hydrophobic and aromatic residues in the substrate binding site create a cavity in which the substrates can comfortably undergo van der Waals and pi-stacking interactions. Consequently, oxidation of the secondary alcohols is restricted to one of the two enantiomers. This study has uncovered the ability of an FAD-containing alcohol oxidase, that is known for oxidizing small primary alcohols, to perform enantioselective oxidations of various secondary alcohols.

Ester Synthesis in Water: Mycobacterium smegmatis Acyl Transferase for Kinetic Resolutions

The acyl transferase from Mycobacterium smegmatis (MsAcT) catalyses transesterification reactions in aqueous media because of its hydrophobic active site. Aliphatic cyanohydrin and alkyne esters can be synthesised in water with excellent and strikingly opposite enantioselectivity [(R);E>37 and (S);E>100, respectively]. When using this enzyme, the undesired hydrolysis of the acyl donor is an important factor to take into account. Finally, the choice of acyl donor can significantly influence the obtained enantiomeric excesses. (Figure presented.).

Enantioconvergent Nucleophilic Substitution Reaction of Racemic Alkyne-Dicobalt Complex (Nicholas Reaction) Catalyzed by Chiral Br?nsted Acid

Catalytic enantioselective syntheses enable a practical approach to enantioenriched molecules. While most of these syntheses have been accomplished by reaction at the prochiral sp2-hybridized carbon atom, little attention has been paid to enantioselective nucleophilic substitution at the sp3-hybridized carbon atom. In particular, substitution at the chiral sp3-hybridized carbon atom of racemic electrophiles has been rarely exploited. To establish an unprecedented enantioselective substitution reaction of racemic electrophiles, enantioconvergent Nicholas reaction of an alkyne-dicobalt complex derived from racemic propargylic alcohol was developed using a chiral phosphoric acid catalyst. In the present enantioconvergent process, both enantiomers of the racemic alcohol were transformed efficiently to a variety of thioethers with high enantioselectivity. The key to achieving success is dynamic kinetic asymmetric transformation (DYKAT) of enantiomeric cationic intermediates generated via dehydroxylation of the starting racemic alcohol under the influence of the chiral phosphoric acid catalyst. The present fascinating DYKAT involves the efficient racemization of these enantiomeric intermediates and effective resolution of these enantiomers through utilization of the chiral conjugate base of the phosphoric acid.

Application of homochiral alkylated organic cages as chiral stationary phases for molecular separations by capillary gas chromatography

Molecular organic cage compounds have attracted considerable attention due to their potential applications in gas storage, catalysis, chemical sensing, molecular separations, etc. In this study, a homochiral pentyl cage compound was synthesized from a condensation reaction of (S,S)-1,2-pentyl-1,2-diaminoethane and 1,3,5-triformylbenzene. The imine-linked pentyl cage diluted with a polysiloxane (OV-1701) was explored as a novel stationary phase for high-resolution gas chromatographic separation of organic compounds. Some positional isomers were baseline separated on the pentyl cage-coated capillary column. In particular, various types of enantiomers including chiral alcohols, esters, ethers and epoxides can be resolved without derivatization on the pentyl cage-coated capillary column. The reproducibility of the pentyl cage-coated capillary column for separation was investigated using nitrochlorobenzene and styrene oxide as analytes. The results indicate that the column has good stability and separation reproducibility after being repeatedly used. This work demonstrates that molecular organic cage compounds could become a novel class of chiral separation media in the near future.

Coupling biocatalysis and click chemistry: One-pot two-step convergent synthesis of enantioenriched 1,2,3-triazole-derived diols

A fully convergent one-pot two-step synthesis of different chiral 1,2,3-triazole-derived diols in high yields and excellent enantio- and diastereoselectivities has been achieved under very mild conditions in aqueous medium by combining a single alcohol dehydrogenase (ADH) with a Cu-catalysed 'click' reaction. The Royal Society of Chemistry 2013.

Asymmetric hydrogenation of alkynyl ketones with the η6- arene/TsDPEN-ruthenium(II) catalyst

Enantioselective hydrogenation of alkynyl ketones catalyzed by Ru(OTf)(TsDPEN)(η6-p-cymene) (TsDPEN = N-(p-toluenesulfonyl)-1,2- diphenylethylenediamine) affords the propargylic alcohols in up to 97% ee. The alkynyl moieties are left intact in most cases. The reaction can be conducted with a substrate-to-catalyst molar ratio as high as 5000 under 10 atm of H 2. The mode of enantioselection is elucidated with the transition state models directed by the CH/π attractive interaction between the substrate and the catalytic species.

Electrical and mechanical anharmonicities from NIR-VCD spectra of compounds exhibiting axial and planar chirality: The cases of (S)-2,3-pentadiene and methyl-d3 (R)- and (S)-[2.2]paracyclophane-4-carboxylate

The IR and Near infrared (NIR) vibrational circular dichroism (VCD) spectra of molecules endowed with noncentral chirality have been investigated. Data for fundamental, first, and second overtone regions of (S)-2,3-pentadiene, exhibiting axial chirality, and methyl-d3 (R)- and (S)-[2.2]paracyclophane-4-carboxylate, exhibiting planar chirality have been measured and analyzed. The analysis of NIR and IR VCD spectra was based on the local-mode model and the use of density functional theory (DFT), providing mechanical and electrical anharmonic terms for all CH-bonds. The comparison of experimental and calculated spectra is satisfactory and allows one to monitor fine details in the asymmetric charge distribution in the molecules: these details consist in the harmonic frequencies, in the principal anharmonicity constants, in both the atomic polar and axial tensors and in their first and second derivatives with respect to the CH-stretching coordinates. Chirality, 2011. 2011 Wiley Liss, Inc. Copyright

Inclusion of aliphatic alcohols in pockets of (S)-threonyl-(S)- phenylglycine using grinding method

Inclusion compounds of a dipeptide, (S)-threonyl-(S)-phenylglycine (Thr-Phg), with several aliphatic alcohols were easily prepared by grinding them in a mortar. Thr-Phg molecules arranged in antiparallel to construct a sheet, and guest alcohols were accommodated in a chiral pocket between the sheets. 3-Butyn-2-ol and 2-butanol were included with moderate enantioselectivity, 57% ee (R) and 49% ee (R), respectively. The role of the hydroxy group of Thr-Phg is not only to construct the unique pocket but also to capture guest alcohols by hydrogen bonding.

PROCESS FOR THE PREPARATIN OF ALKYNOLS

Process for the preparation of an alkynol with formula HC=C-C(OH)-R2 (formula 2) wherein R2 represents methyl, halomethyl or ethyl, wherein the corresponding silyl-protected alkynol ester with formula 1 (1) wherein R1 represents H, or an optionally substituted alkyl, an optionally substituted alkenyl or an optionally substituted (hetero)aryl group, R2 is as defined above and A3Si represents a trisubstituted silyl group wherein each A independently represents anoptionally substituted alkyl or an optionally substituted (hetero)aryl group, in the presence of water and at least an equivalent amount of amine functionalities is converted into the alkynol with formula 2. Preferably, the amount of water is between 0.5 and 3 equivalents calculated with respect to the amount of silyl-protected alkynol ester with formula (1).