73522-97-1

Upstream product

• 13531-82-3 4-methylpent-1-yn-3-one 
• 108-05-4 vinyl acetate 
• 565-68-4 4-methylpent-1-yn-3-ol 
• 108-22-5 Isopropenyl acetate 
• 122-79-2 Phenyl acetate 
• 141-78-6 ethyl acetate 
• 153123-13-8 (S_S,R)-(E)-4-methyl-2-(p-tolylsulfinyl)-1-(trimethylsilyl)-1-penten-3-ol 

Downstream Products

• 1346685-89-9 (R)-triisopropyl[(4-methylpent-1-yn-3-yl)oxy]silane 
• 565-69-5 ethyl isopropyl ketone 
• 70492-65-8 (S)-2-methyl-3-pentanol 
• 89046-82-2 ((S)-4-Methyl-pent-1-yne-3-sulfonyl)-benzene 
• 89046-82-2 (4-Methyl-pent-1-yne-3-sulfonyl)-benzene 
• 89104-09-6 (4-Methyl-penta-1,2-diene-1-sulfonyl)-benzene 
• 77084-83-4 (4-methylpent-1-yn-3-yl)(phenyl)sulfane 
• 98973-94-5 (1S,3R)-2,2-Dimethyl-3-((R)-2-methyl-1-p-tolyloxythiocarbonyloxy-propyl)-cyclopropanecarboxylic acid methyl ester 
• 750775-69-0 (4-Methyl-penta-1,2-diene-1-sulfinyl)-benzene 
• 89046-81-1 ((S)-1-Isopropyl-prop-2-ynylsulfanyl)-benzene 
• 77084-82-3 4-methyl-1,2-pentadienyl phenyl sulfide 

Relevant academic research and scientific papers

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.).

Total syntheses of the dipyrrolobenzoquinone (+)-terreusinone enabled by an evaluation of 4-methylpent-1-yn-3-ols in the Larock indole synthesis

The Larock indolization between 4-methylpent-1-yn-3-ols (alkynols) and ortho-bromo and ortho-iodoanilines has been studied. Although the unprotected alkynol was an unviable substrate for the annulation reaction, protected derivatives did proceed to the indole products. Interestingly, this reaction does not appear to occur by the widely accepted mechanism for the Larock indolization of internal alkynes, but by the initial formation of a cross-coupled arylalkyne followed by 5-endo-dig cyclization. Importantly, when a chiral alkynol is used, the stereochemical integrity is retained in the indole product. Although this methodology could not be successfully extended to a double Larock indolization approach to terreusinone, two separate total syntheses evolved from these studies: A bidirectional, double Sonogashira-hydroamination approach and a one-pot Larock indolization- Sonogashira coupling followed by hydroamination. This work has not only confirmed the gross structure and absolute configuration of the photoprotecting natural product terreusinone, but also uncovered several novel applications of known reaction conditions that should find broad applications in the field of heteroaromatic construction.

Total synthesis of bafilomycin A1

A convergent synthesis of bafilomycin A1, a potent inhibitor of V-type ATPases, is presented. The synthesis relies on the zinc triflate mediated diastereoselective addition of a complex enyne to a sensitive aldehyde as the key fragment coupling. A ruthenium-catalyzed trans-reduction of the resulting propargylic enyne efficiently installs the required C10-C13 trans,trans-diene subunit, implementing an alternative strategy to traditional palladium-catalyzed cross-coupling strategies. A highly selective oxidation of a secondary hydroxyl group in a triol sets the stage for the completion of the synthesis. Copyright

Total synthesis of the photoprotecting dipyrrolobenzoquinone (+)-terreusinone

The first synthesis of (+)-terreusinone 1, a dipyrrolobenzoquinone with a potent UV-A protecting capability, is described. Key transformations include a one-pot Larock indolization-Sonogashira coupling reaction and the hydroamination of an unsubstituted o

Pheromone synthesis. Part 243: Synthesis and biological evaluation of (3R,13R,1′S)-1′-ethyl-2′-methylpropyl 3,13-dimethylpentadecanoate, the major component of the sex pheromone of Paulownia bagworm, Clania variegata, and its stereoisomers

All of the four stereoisomers of (1′S)-1′-ethyl-2′-methylpropyl 3,13-dimethylpentadecanoate, the major component of the female sex pheromone of Clania variegata, were synthesized by employing olefin cross metathesis as the key reaction and starting from (R)- or (S)-2-methyl-1-butanol, (R)- or (S)-citronellal, and (S)-2-methyl-3-pentanol. Their bioassay revealed the (3R,13R,1′S)-isomer as the bioactive one, whose more efficient synthesis was achieved in two different ways by employing Wittig reaction as the key step.

Synthesis of all the four stereoisomers of (1′S)-1-ethyl-2-methylpropyl 3,13-dimethylpentadecanoate, the major component of the sex pheromone of Paulownia bagworm, Clania variegata

All the four stereoisomers of (1′S)-1-ethyl-2-methylpropyl 3,13-dimethylpentadecanoate, the major component of the sex pheromone of Clania variegata, were synthesized by starting from (R)- or (S)-2-methylbutan-1-ol, (R)- or (S)-citronellal, and (S)-2-methylpentan-3-ol. Olefin cross metathesis was employed as the key reaction.

Kinetic resolution of propargylic and allylic alcohols by Candida antarctica lipase (Novozyme 435)

A number of chiral propargylic and allylic alcohols were resolved by lipase-catalyzed kinetic resolution (Novozyme 435). In some cases the enantiomeric excess was high (up to >99%).

Convenient Preparation of Optically Pure Propargylic Alcohols Using 2-(Trimethylsilyl)vinyl Sulfoxide As A Novel Chiral Synthon

Both enentiomers of optically pure propargylic alcohols are conveniently prepared by the reaction of α-vinyl anion of 2-(trimethylsilyl)vinyl p-tolyl sulfoxide with aldehydes and subsequent either desilylsulfination or thermal elimination of the sulfinyl group.

Selective Reductions. 37. Asymmetric Reduction of Prochiral Ketones with B-(3-Pinanyl)-9-borabicyclononane

The chiral trialkylborane B-(3-pinanyl)-9-borabicyclononane, either with the neat reagents or concentrated solutions, 2 M, reduces a wide range of prochiral carbonyl compounds with good to excellent asymmetric induction.Reduction of simple dialkyl ketones, 2-butanone, 2-octanone, 3-methyl-2-butanone, and 3,3-dimethyl-2-butanone, yields the corresponding alcohols with 43percent, 48percent, 62percent, and 0.7percent asymmetric induction.Acetophenone is reduced to 1-phenylethanol in 85percent ee.The α,β-unsaturated ketones 3-buten-2-one, 1-acetyl-1-cyclohexene, 3-methyl-2-cyclohexenone, and trans-4-phenyl-3-buten-2-one are reduced to the corresponding allylic alcohols with 57percent, 64percent, 11percent, and 97percent asymmetric induction, respecticvely.The α,β-conjugated acetylenic ketones 3-butyn-2-one, 4-methyl-1-pentyn-3-one, and 4-phenyl-3-butyn-2-one underwent a rapid reduction to afford the corresponding propargylic alcohols with 79percent, 99percent, and 91percent enantiomeric purities.The α-haloalkyl aromatic ketones α-chloroacetophenone, α-bromoacetophenone, α-iodoacetophenone, α,p-dibromoacetophenone, α-bromo-p-cyanoacetophenone,α-bromo-2'-acetonaphthone,and α,α,α-trifluoroacetophenone afforded the corresponding halohydrins with 96percent,93percent,93percent,96percent,96percent,90percent,and35percent enantiomeric purities, respectively.The corresponding aliphatic analogue 1-bromo-3-methyl-butanone gave the halohydrin in 66percent ee.The other isomer of this ketone, 3-bromo-3-methyl-2-butanone, failed to undergo reduction.Both the aliphatic and aromatic α-keto esters underwent rapid reduction to give the corresponding α-hydroxy esters with excellentenantiomeric excesses.Thus, methyl, ethyl, isopropyl, and tert-butyl pyruvates afforded the corresponding lactates with 86percent,83percent,78percent, and 92percent ee at 25 deg C,respectively.Lowering the reaction temperature to 0 deg C gave the tert-butyl lactate in 100percent ee.Other aliphatic α-keto esters such as metyl and ethyl 2-oxopentanoates, methyl 3-methyl-2-oxobutanoate, and ethyl 4-methyl-2-oxopentanoate were reduced to the corresponding α-hydroxy esters with 96percent, 96percent, 11percent, and 82percent ee.The methyl, isopropyl, and tert-butyl benzoylformates were reduced to the corresponding mendelic esters with 90percent, 96percent and 100percent ee, respectively.The reduction of the β-keto esters, however, proceeded slowly and ethyl acetoacetate gave the corresponding alcohol with 55percent ee.