Recent Advances in the Synthesis and Chemistry of Nitronates

Due to their availability and versatile reactivity, nitronates have become important building blocks in the stereoselective synthesis of bioactive molecules. This short review provides a summary of recent developments on the synthesis, chemistry and applications of O-alkyl and O-silyl nitronates. 1 Introduction 2 Approaches to the Synthesis of Nitronates 2.1 Synthesis of Six-Membered Cyclic Nitronates 2.1.1 Formal [4+2] Approaches 2.1.2 Formal [3+3] Approaches 2.1.3 Other Approaches 2.2 Synthesis of Five-Membered Cyclic Nitronates 2.2.1 Formal [3+2] Approaches 2.2.2 Formal [4+1] Approaches 2.2.3 Oxidation Approaches 3 Chemistry of Nitronates 3.1 Nitronates as α-C-Nucleophiles 3.2 Nitronates as α-C-Electrophiles 3.3 Nitronates in [3+n]-Annulation Reactions 3.4 Reactions Involving the β-Carbon Atom of Nitronates 3.5 Miscellaneous Transformations 4 Conclusion

[1]  U. Koert,et al.  Metal‐Catalyzed Synthesis of Functionalized 1,2,4‐Oxadiazoles from Silyl Nitronates and Nitriles , 2017 .

[2]  H. Uno,et al.  OXIDATIVE SYNTHESIS OF ISOXAZOLINE-N-OXIDE FROM OPTICALLY ACTIVE NITRO ALCOHOLS , 2016 .

[3]  Takuji Kawamoto,et al.  An oxidative cyclopropanation reaction of primary nitro compounds using Fe2O3 , 2016 .

[4]  Kwunmin Chen,et al.  Dihydrooxazine N-Oxide Intermediates as Resting States in Organocatalytic Kinetic Resolution of Functionalized Nitroallylic Amines with Aldehydes. , 2016, Organic letters.

[5]  H. Uno,et al.  Asymmetric Synthesis of Bicyclic Nitrocyclopropanes from Primary Nitro Compounds and Stereoselective Formation of Tetrahydro-2H-cyclopenta[b]furans via Ring Expansion/Cyclization Reaction. , 2016, The Journal of organic chemistry.

[6]  S. Kurbatov,et al.  Sequential SNAr and Diels–Alder reactivity of superelectrophilic 10π heteroaromatic substrates , 2016 .

[7]  P. Jiao,et al.  Silyl Nitronate Cycloadditions Catalyzed by Cu(II)-Bisoxazoline. , 2015, The Journal of organic chemistry.

[8]  N. Paparoidamis,et al.  A new method for functionalizing α,γ‐dinitro compounds at the β‐position: application to the cyclization of β‐alkoxy‐α,γ‐dinitro compounds , 2014 .

[9]  D. Stalke,et al.  Donor-substituted nitrocyclopropanes: immediate ring-enlargement to cyclic nitronates. , 2013, Organic letters.

[10]  Y. Nelyubina,et al.  Synthesis of PDE IVb Inhibitors. 3. Synthesis of (+)-, (-)-, and (±)-7-[3-(cyclopentyloxy)-4-methoxyphenyl]hexahydro-3H-pyrrolizin-3-one via reductive domino transformations of 3-β-carbomethoxyethyl-substituted six-membered cyclic nitronates. , 2012, The Journal of organic chemistry.

[11]  A. Kamimura,et al.  Stereoselective synthesis of 1-nitrobicyclo[3.1.0]hexanes and fused isoxazoline-N-oxides from primary nitro compounds. , 2012, The Journal of organic chemistry.

[12]  M. Kodess,et al.  Unexpected spontaneous ring-contraction rearrangement of trifluoromethylated 1,2-oxazine N-oxides to 1-pyrroline N-oxides , 2011 .

[13]  D. Werz,et al.  Ring-enlargement reactions of donor-acceptor-substituted cyclopropanes: which combinations are most efficient? , 2011, Organic letters.

[14]  O. Kwon,et al.  Tandem 6pi-electrocyclization and cycloaddition of nitrodienes to yield multicyclic nitroso acetals. , 2010, Journal of the American Chemical Society.

[15]  V. V. Kachala,et al.  Superelectrophilic nature of 4,6-dinitrobenzo[c]isoxazole (4,6-dinitroanthranil) in [4 + 2]-cycloaddition reactions and σH-complex formation , 2010 .

[16]  D. MacMillan,et al.  Enantioselective aldehyde alpha-nitroalkylation via oxidative organocatalysis. , 2009, Journal of the American Chemical Society.

[17]  Yi-Ju Cao,et al.  A new entry to cascade organocatalysis: reactions of stable sulfur ylides and nitroolefins sequentially catalyzed by thiourea and DMAP. , 2008, Journal of the American Chemical Society.

[18]  H. Mayr,et al.  Thermodynamic stability and reactivity of silylated bis(oxy)iminium ions. , 2007, The Journal of organic chemistry.

[19]  T. Nemoto,et al.  Pd-catalyzed asymmetric allylic alkylation with nitromethane using a chiral diaminophosphine oxide: (S,RP)-Ph-DIAPHOX. Enantioselective synthesis of (R)-preclamol and (R)-baclofen , 2006 .

[20]  Y. Tohda,et al.  The nitroalkene showing dual behaviors in the same reaction system , 2005 .

[21]  G. P. Howell,et al.  An asymmetric nitro-Mannich reaction applicable to alkyl, aryl, and heterocyclic imines. , 2005, The Journal of organic chemistry.

[22]  N. Zefirov,et al.  Catalytic cyclopropanation of methylenecyclobutanes using ethyl nitrodiazoacetate. Synthesis of spirohexane amino acids , 2003 .

[23]  Ryan P. Wurz,et al.  Synthesis of α‐Nitro‐α‐diazocarbonyl Derivatives and Their Applications in the Cyclopropanation of Alkenes and in O ? H Insertion Reactions , 2002 .

[24]  A. Padwa,et al.  Synthetic applications of 1,3-dipolar cycloaddition chemistry toward heterocycles and natural products , 2002 .

[25]  L. Maini,et al.  d-Mannitol as the Chiral Source for the EPC Synthesis of Both Enantiomers of 3-Ethoxycarbonyl-4-hydroxy-2-isoxazolines and Highly Functionalized Tricyclic Systems , 1998 .

[26]  K. Torssell Nitrile Oxides, Nitrones and Nitronates in Organic Synthesis: Novel Strategies in Synthesis , 1988 .