84051-52-5

Upstream product

• 88930-43-2 (6β,20S,23Z)-20-hydroxy-6-methoxy-24-(phenylthio)-24-(trimethylsilyl)-3α,5α-cyclochol-23-ene 
• 67-64-1 acetone 
• 32249-55-1 (20S)-3α,5-cyclo-20-formyl-6β-methoxy-5α-pregnane 
• 78905-13-2 phenyl 1-(trimethylsilyl)prop-2-en-1-yl sulfide 
• 35961-41-2 1-((3S,10R,13S,17S)-10,13-dimethyl-3-((tetrahydro-2H-pyran-2-yl)oxy)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl)ethanone 
• 84051-47-8 (Z)-2-((1aR,3aR,3bS,5aS,6S,8aS,8bS,10R,10aR)-10-Methoxy-3a,5a-dimethyl-hexadecahydro-cyclopenta[a]cyclopropa[2,3]cyclopenta[1,2-f]naphthalen-6-yl)-5-phenylsulfanyl-5-trimethylsilanyl-pent-4-en-2-ol 
• 32249-55-1 6β-methoxy-3α,5α-cyclopregnan-20-one 

Relevant academic research and scientific papers

Dienol Rearrangements Catalyzed by Nickel Chloride

The rearrangement of dienols R2C(OH)CH=CHC(X)=CR2 which possess a nonterminal, arylthio or alkylthio substituent was effected by using nickel chloride in aqueous tert-butyl alcohol at 60 deg C to furnish the vicinally substituded dienol R2C=CHCH=C(X)CR2(OH).Application of this rearrangement to 24-(methylthio)cholesta-5,22,24-trien-20-ol provided 24-(methylthio)cholesta-5,20(22),23-trien-25-ol and formed the basis for a new, five-step synthesis of (20R)-25-hydroxycholesterol from pregnenolone tetrahydropyranyl ether.The rearrangement process appeared to be driven by the relief of unfavorable steric interactions between the quaternary C-13 and C-20 centers in steroids and influenced by the nature of the nickel(II) catalyst.The sulfur-containing substituent was not a prerequisite for the rearrangement since the desulfurized dienols underwent an analogous rearrangement.Preparation of these desulfurized dienols involved the use of a Raney nickel catalyst deactivated by heating in decalin.This catalyst selectively desulfurized vinyl thioethers to olefins.