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Transition Metal‐Catalyzed Synthesis of 3‐Coumaranone‐Containing NH‐Aziridines from 2 H ‐Azirines: Nickel(II) versus Gold(I)
Author(s) -
Sakharov Pavel A.,
Rostovskii Nikolai V.,
Khlebnikov Alexander F.,
Khoroshilova Olesya V.,
Novikov Mikhail S.
Publication year - 2019
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201900366
Subject(s) - chemistry , aziridine , catalysis , substituent , nucleophile , yield (engineering) , transition metal , medicinal chemistry , steric effects , organic chemistry , ring (chemistry) , materials science , metallurgy
A catalytic nucleophilic addition reaction of 3‐hydroxybenzofuran‐2‐carboxylic acid derivatives to 2 H ‐azirines for the high‐yield synthesis of NH‐aziridines with a 3‐coumaranone substituent has been developed. The Ph 3 PAuNTf 2 ‐catalyzed reaction is diastereoselective to give predominantly ( RS , SR )‐isomer of aziridine in good yield. The Ni(hfacac) 2 ‐catalyzed reaction affords aziridines in up to 98% yield and low or moderate diastereoselectivity, which in some cases is opposite to that observed for the gold(I)‐catalyzed reaction. The Ph 3 PAuNTf 2 works well for sterically hindered azirines as well as benzofurans bearing electron‐withdrawing groups, whereas Ni(hfacac) 2 is the catalyst of choice for the preparation of aziridines having diazoacetyl substituent. The latter compounds can serve as substrates for the synthesis of fused aziridines via Buchner ring expansion reaction.