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Article Abstract
Stereoselective reduction of C-20 ketone of vitamin D CD-ring precursor using Corey's CBS reagents, (R)-(+)-2-methyl-CBS-oxazaborolidine and (S)-(-)-2-methyl-CBS-oxazaborolidine, led to the (20S)-alcohol 5 and (20R)-epimer 4 in approximately 17:1 selectivity. A new synthetic approach to the 22-oxa-25-hydroxy Grundmann's ketone 11 was developed through the Williamson etherification of (20S)-alcohol 5 with 1-bromomethyl-2,2-dimethyloxirane, followed by regioselective reductive epoxide ring opening with LiAlH4, the removal of the silyl protecting group by TBAF, and the environmentally benign TEMPO-mediated oxidation using inexpensive Oxone as a co-oxidizing agent. The preparation of drug maxacalcitol was achieved on gram scale by the convergent Lythgoe coupling via Wittig-Horner reaction of the A-ring phosphine oxide synthon with the CD-ring fragment.
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| http://dx.doi.org/10.1016/j.steroids.2014.07.005 | DOI Listing |
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