51606-50-9Relevant articles and documents
Selective Isomerization via Transient Thermodynamic Control: Dynamic Epimerization of trans to cis Diols
Macmillan, David W. C.,Oswood, Christian J.
, p. 93 - 98 (2022/01/03)
Traditional approaches to stereoselective synthesis require high levels of enantio- and diastereocontrol in every step that forms a new stereocenter. Here, we report an alternative approach, in which the stereochemistry of organic substrates is selectivel
Chemoenzymatic approaches to the synthesis of the (1S,2R)-isomer of benzyl 2-hydroxycyclohexanecarboxylate
Tsunekawa, Ryuji,Hanaya, Kengo,Higashibayashi, Shuhei,Shoji, Mitsuru,Sugai, Takeshi
, p. 84 - 89 (2017/12/06)
We examined ten strains of cultured whole-cell yeasts for the asymmetric reduction of commercially available ethyl 2-oxocyclohexanecarboxylate, and found that the (1S,2S)-stereoisomer of ethyl 2-hydroxycyclohexanecarboxylate was the major stereoisomer produced by Williopsis californica JCM 3600. The ethyl group of the ester was then substituted with a benzyl group with low volatility and increased hydrophobicity to facilitate the isolation of the expected product. Incubation with W. californica furnished benzyl (1S,2S)-2-hydroxycyclohexanecarboxylate (>99.9% ee) in 51.0% yield together with its (1R,2S)-isomer (>99.9% ee) in 35.4% yield. Upon treatment of the same substrate bearing the benzyl ester with a screening kit of purified overexpressed carbonyl reductases (Daicel Chiralscreen OH), two enzymes (E031, E078) furnished the (1R,2S)-isomer as the major product. With another enzyme (E007), the (1S,2R)-isomer was obtained, but its ee was very low (25.6%). The highly enantiomerically enriched (1S,2S)-isomer obtained by W. californica was transformed to the (1S,2R)-isomer (>99.9% ee), whose availability until now has been low, in 43.3% yield over two steps involving tosylation and subsequent inversive attack with tetrabutylammonium nitrite.
Regioselective mono-deprotection of di-ferf-butylsilylene acetal derived from 1,3-diol with ammonium fluoride
Ohtawa, Masaki,Tomoda, Hiroshi,Nagamitsu, Tohru
, p. 113 - 118 (2014/02/14)
Here we report a novel and efficient method for the regioselective mono-deprotection of di-terf-butylsilylene acetals derived from 1,3-diols consisting of primary and secondary alcohols. The ammonium fluoride-mediated reactions of pyripyropene A derivative, thymidine and uridine derivatives, methyl β-D-glucofuranoside, and pyranoside derivatives each gave the corresponding primary alcohol with high regioselectivity.
