THE NITRO GROUP IN ORGANIC SYNTHESIS

By ANDREW ANDERSON

CONTENTS 1 INTRODUCTION 2 PREPARATION OF NITRO COMPOUNDS 2 1 NITRATION OF HYDROCARBONS / 44 38$& % J ! 44 3'$ J 44! 3& $% % J 44 3' J 44E 0A J " 44" $03'$% J 2 2 SYNTHESIS OF NITRO COMPOUNDS BY OXIDATION / 44 C%$038 J 44 C%$0C8 J 3 THE NITRO-ALDOL (HENRY) REACTION 3 1 PREPARATION OF ?-NITRO ALCOHOLS / 3 2 DERIVATIVES FROM ?-NITRO ALCOHOLS / $ J * 3 3 STEREOSELECTIVE HENRY REACTIONS AND APPLICATIONS TO ORGANIC SYNTHESIS / 4 MICHAEL ADDITION 4 1 ADDITION TO NITROALKENES / 44 I $3%%0$8 %& J 44 I $3%%0$8& $%D 07$& J * 44! I $3%%0 $ %& J *E 4 2 ADDITION AND ELIMINATION REACTION OF ?-HETEROSUBSTITUTED NITROALKENES / 4 3 MICHAEL ADDITION OF NITROALKANES / 4!4 8&$3%% J ! 4!4 $8&$3%% J ! 4 4 ASYMMETRIC MICHAEL ADDITION / 44 $3'$% $ % J E 44 $ $$ J * 5 ALKYLATION, ACYLATION, AND HALOGENATION OF NITRO COMPOUNDS 5 1 ALKYLATION OF NITRO COMPOUNDS / 5 2 ACYLATION OF NITROALKANES / 5 3 RING CLEAVAGE OF CYCLIC ?-NITRO KETONES (RETRO-ACYLATION) / 5 4 ALKYLATION OF NITRO COMPOUNDS VIA ALKYL RADICALS / 5 5 ALKYLATION OF NITRO COMPOUNDS USING TRANSITION METAL CATALYSIS / E4E4 $%;8?$ J !* E4E4 ,% $$?%3& 3'$0 % J 5 6 ARYLATION OF NITRO COMPOUNDS / 5 7 INTRODUCTION OF HETEROATOMS TO NITROALKANES / 6 CONVERSION OF NITRO COMPOUNDS INTO OTHER COMPOUNDS 6 1 NEF REACTION (ALDEHYDES, KETONES, AND CARBOXYLIC ACIDS) / "44 C%$ 9% J " "44! 7%& 9% J " "44 =& 0$' $ % J "E 6 2 NITRILE OXIDES AND NITRILES / 6 3 REDUCTION OF NITRO COMPOUNDS INTO AMINES / 7 1 R–NU FROM R–NO2 / 44 7$%&$7$&#7( J * 44 &,& J *E 44! $8&$& &7$& J 44 3&7$$ 8 J 7 2 R–H FROM R–NO2 / 44 7$%&$=$ J 2! 44 &=$ J 7 3 ALKENES FROM R–NO2 / 4!4 7$%&$+8$ J 4!4 &+8$0 % J * 8 CYCLOADDITION CHEMISTRY OF NITRO COMPOUNDS 8 1 DIELS-ALDER REACTIONS / *44 $'- = J ! *44 388&=3%7$& J ! 8 2 1,3-DIPOLAR CYCLOADDITION / *44 J *44 C% J E* *44! $ J " 8 3 NITROALKENES AS HETERODIENES IN TANDEM [4+2]/[3+2] CYCLOADDITION / *4!4 $'$% J E *4!4 ;$%8KLMJK!LM &$%%0$' J 9 NUCLEOPHILIC AROMATIC DISPLACEMENT 9 1 SNAR / 9 2 NUCLEOPHILIC AROMATIC SUBSTITUTION OF HYDROGEN (NASH) / 244 $& J ! $%$8& J !" 244! &$0&&& % J !* 10 SYNTHESIS OF HETEROCYCLIC COMPOUNDS 10 1 PYRROLES / 10 2 SYNTHESIS OF INDOLES / 10 3 SYNTHESIS OF OTHER NITROGEN HETEROCYCLES /