66613-24-9

Upstream product

• 60466-66-2 (Z)-2-methoxy-1-(phenylthio)-1,3-butadiene 
• 20614-49-7 1-phenylsulfanyl-but-3-en-2-ol 
• 127-08-2 potassium acetate 
• 75384-19-9 1-diazo-4-(phenylthio)butan-2-one 
• 64-19-7 acetic acid 
• 13307-75-0 (phenylthio)methyllithium 
• 100-68-5 methyl-phenyl-thioether 
• 3536-96-7 vinylmagnesium chloride 
• 191731-37-0 N-methoxy-N-methyl-2-(phenylthio)acetamide 

Downstream Products

• 78742-70-8 4-phenylamino-1-phenylthiobutan-2-one 
• 203392-58-9 S-tert-butyl (2R)-[(1R,2R)-3-oxo-2-(3-oxo-4-phenylthiobutyl)cyclopentyl]-4-[(4S)-2,2,5,5-tetramethyl-1,3-dioxolan-4-yl]butanethioate 
• 485321-43-5 2-[(phenylthio)methyl]-2-vinyl[1,3]dioxolane 
• 1061162-24-0 C₂₆H₂₇NO₃S₂ 

Relevant academic research and scientific papers

Multikilogram Synthesis of a Potent Dual Bcl-2/Bcl-xL Antagonist. 2. Manufacture of the 1,3-Diamine Moiety and Improvement of the Final Coupling Reaction

This paper describes the synthesis of kilogram quantities of the sulfonamide moiety 3 involved in a coupling reaction with acid moiety 2 to provide batches of drug candidate 1 for preclinical studies and first-in-human clinical trials. A first approach relying on a chiral separation furnished the desired enantiomer of 1,3-diamine 20, precursor of sulfonamide 3. An enantiomeric synthesis of 20 using the Ellman's chiral auxiliary coupled with an aza-Reformatsky reaction to control the stereochemistry is also discussed. Coupling conditions of the final step involving EDCI to provide 1 under a cGMP process are detailed. An alternative approach using N-(1-methanesulfonyl)benzotriazole is also presented.

Catalytic enantioselective annulation using phenylsulfanylmethyl vinyl ketone. An approach to trans-hydrindane building blocks for ent-vitamin D3 synthesis

An enantioselective synthesis of the ent-vitamin D3 northern portion building block is presented. The key step involves phenylalanine-catalyzed annulation of 2-methylcyclopent-2-en-1-one with phenylsulfanylmethyl vinyl ketone.

Preparation and Reactions of Novel Cyclic β-Oxosulphonium Salts obtained by the Acid-induced Cycisation of 1-Diazo-ω-phenylthio-2-alkanones

With perchloric acid, the diazo-ketones PhSnCOCHN2 (1a)-(1d) give the corresponding cyclic β-oxosulphonium salts (2a)-(2d); the p-chlorophenyl analogue of (2d) was similarly prepared.The salts (2a), (2c), and (2d) react with triphenylphosphine at C(2) to give the acyclic phosphonium salts (3a), (3c), and (3d) and, analogously, with potassium O-ethyl dithiocarbonate to give the corresponding acyclic O-ethyl dithiocarbonates (3f), (3g), and (3h).All the reactions of the salt (2b) with nucleophiles gave either 1-phenylthiobut-3-en-2-one (11) or products of its Michael addition.Salts (2c) and (2d) with sodium methoxide in methanol provide, respectively, methyl ω-phenylthio-butanoate and -pentanoate in a process that involves the loss of a methylene group.These and other reactions are considered to proceed via ylide intermediates; the intermediate derived by the deprotonation of (2d) being isolated, whereas that from (2c) rearranged to give 3-phenylthiocyclopentanone.

REACTIONS OF α-DIAZO KETONES. IV. S-5 PARTICIPATION AND β-ELIMINATION IN THE ACETOLYSIS OF 4-ARYLTHIO- AND 4-ARALKYLTHIO-1-DIAZO-2-BUTANONES

The acetolyses of α-diazo ketones 2a-d, bearing a thioether group on the β'-carbon have been studied in neat AcOH and in the presence of acetate.All these reactions lead to products arising from the 1,4-shift of the thioether group, normal substitution being only a secondary pathway, particularly in the case of 2d, which almost exclusively undergoes fragmentation to benzhydryl acetate and 3-oxotetrahydrothiophene.The mechanisms involved are discussed.

RAPID, HIGH YIELD CLEAVAGE OF ENOL AND DIENOL METHYL ETHERS UNDER MILD CONDITIONS USING CHLOROTRIMETHYLSILANE/SODIUM IODIDE

A number of enol and dienol methyl ethers are rapidly cleaved to aldehydes and ketones in quantitative yields by the use of chlorotrimethylsilane/sodium iodide.