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NaBH 3 CN: A Janus Substitute for Tin‐Free Radical‐Based Reactions
Author(s) -
Guiard Julie,
Rahali Yaniss,
Praly JeanPierre
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201402441
Subject(s) - chemistry , radical , reagent , radical initiator , azobisisobutyronitrile , tin , radical cyclization , medicinal chemistry , radical substitution , reactivity (psychology) , photochemistry , free radical reaction , inert gas , ionic bonding , organic chemistry , ion , medicine , alternative medicine , pathology , polymerization , polymer
Abstract Beside showing that thermal radical reactions (reduction, Giese reaction) are efficient if bromo‐/iodosugars are treated with NaBH 3 CN and 2,2″‐azobisisobutyronitrile, we explored new initiation conditions on the basis of Cu I salts (≤0.5 equiv.) supposed to produce radicals from organobromides through a set. This was confirmed, as at about 50 °C under an inert atmosphere acetobromoglucose was reduced to the rearranged 2‐deoxyglucose and as N ‐allyl α‐bromoamides reacted, depending on the conditions, either by reductive cyclization or atom‐transfer radical cyclization. A related cyclization occurred upon using Cu(OAc) 2 . This and other assays showed the reduction by NaBH 3 CN of Cu II salts, either added or formed in situ. Having both ionic and radical reactivity, NaBH 3 CN appears as a Janus reagent that may be useful for tin‐free radical chemistry under mild and very simple conditions.