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ChemComm
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DOI: 10.1039/C5CC02374B
COMMUNICATION
Journal Name
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undergoes regioselective ring opening with DMF to give the
corresponding iodo intermediate
stereoselective displacement with azide ion to form species II.
This on hydrolysis affords syn azido alcohols . On the other
hand, under aq. H2O2 condition, the iodo intermediate is
hydrolyzed in situ to form iodoformate . The proposed species
III formed from by the anchimeric assistance shown by the
formate group, reacts with azide anion in a regioselective
manner to give anti azido alcohol with the liberation of iodide
I followed by subsequent
2
I
5
5
4
5
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in the catalytic cycle.
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The application of this novel method is amply illustrated in
the concise total synthesis of (±)ꢀchloramphenicol (9
),23 an
antibiotic drug and (±)ꢀcytoxazone (11),24 a cytokine modulator.
1,2ꢀsyn azido alcohol 2m, prepared by the present protocol was
subjected to simple reductionꢀprotection sequence
8
9
Lett., 2002, 4, 343-345.
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Scheme 4. Total Synthesis of (±)-chloramphenicol and (±)-cytoxazone
followed by regioselective nitration gave (±)ꢀchloramphenicol
(9) in 71% yield. Also, azidodiol 3n, prepared from 1n using
condition B, on reductionꢀBoc protection sequence, gave
aminodiol 10 in 76% yield, which under basic condition underꢀ
went cyclization to give (±)ꢀcytoxazone (11) in 90% yield
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(
Scheme 4).
To summarize, we have developed, for the first time, regioꢀ and
diastereoselective azidohydroxylation of alkenes to give vicinal
azidoalcohols in high yields. The regioꢀ and stereodivergence
observed in the process is driven by the oxidants chosen in
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DMF is crucial for regiodivergence and acts as an
Oꢀsource in
this azidohydroxylation reaction. This methodology has
successfully been applied to the concise syntheses of (±)ꢀ
chloramphenicol and (±)ꢀcytoxazone. We believe that this mild,
environmentally benign and operationally simple method would
find tremendous application in streamlining the synthesis of
various drugs and synthetically useful intermediates. Chiral
version of this azidohydroxylation process is currently
underway in our laboratory and will be reported in due course.
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4 | J. Name., 2012, 00, 1-3
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