Acyl Azides: Versatile Compounds in the Synthesis of Various Heterocycles

Balcı, Metin
Carbon-nitrogen bond formation is one of the most important reactions in organic chemistry. Various synthetic strategies for the generation of C-N bonds are described in the literature. For example, primary amines can be easily synthesized by the thermal decomposition of an acyl azide to an isocyanate, i.e. the Curtis rearrangement, followed by hydrolysis; the Curtius rearrangement has been used extensively. Furthermore, the advantage of the Curtius rearrangement is the isolation of acyl azides as well as the corresponding isocyanates. The isocyanates can be converted into various nitrogen-containing compounds upon reaction with various nucleophiles that can be used as important synthons for cyclization, in other words, for the synthesis of heterocycles. Therefore, this review demonstrates the importance of acyl azides not only in the synthesis acyclic systems, but also in the synthesis of various nitrogen-containing heterocycles. 1 Introduction 2 Synthesis of Acyl Azides 2.1 Acyl Azides from Carboxylic Acid Derivatives 2.2 Acyl Azides by Direct Transformation of Carboxylic Acids 2.3 Acyl Azides from Aldehydes 2.4 Carbamoyl Azides from Haloarenes, Sodium Azide, and N -Formylsaccharin 3 Mechanism of Formation of Isocyanates 4 Synthesis of Diacyl Azides 5 Synthetic Applications 5.1 Synthesis of Pyrimidinone Derivatives 5.2 Dihydropyrimidinone and Isoquinolinone Derivatives 5.3 Synthesis of Tetrahydroisoquinoline Skeleton 5.4 Synthesis of Five-Membered Heterocycles 5.5 Heterocycles Synthesized Starting from Homophthalic acid 5.6 Heterocycles Synthesized from 2-(Ethoxycarbonyl)nicotinic Acid 5.7 Formation of Aza-spiro Compounds 5.8 Parham-Type Cyclization 5.9 Diazepinone Derivatives 5.10 Synthesis of Pyridine Derivatives 5.11 Synthesis of Indole Derivatives 6 Miscellaneous 7 Conclusion


Benzaldehyde Lyase-Catalyzed Direct Amidation of Aldehydes with Nitroso Compounds
Ayhan, Peruze; Demir, Ayhan Sıtkı (Wiley, 2011-03-07)
Benzaldehyde lyase from the Pseudomonas fluorescens catalyzes the reaction of aromatic aldehydes with nitroso compounds and furnishes N-arylhydroxamic acids in high yields. Aromatic aldehydes and benzoins are converted into enamine-carbanion-like intermediates prior to their reaction with nitroso compounds. The kinetic resolution of rac-2-hydroxy-1,2-diphenylethanones furnished (S)-benzoins and arylhydroxamic acids with high enantioselectivities and conversions.
Boron trifluoride mediated Prins reaction of methylene diacetate with styrenes. One-pot synthesis of 3-chloro-3-arylpropanols
İŞLEYEN, ALPER; Doğan, Özdemir (Georg Thieme Verlag KG, 2006-05-03)
A one-pot procedure was developed for the synthesis of 3-chloro-3-arylpropanols, which are important starting materials for the synthesis of biologically active benzanilide derivatives. Styrenes were reacted with methylene diacetate in the presence of boron trifluoride to give the corresponding 3-chloro-3-arylpropanols in 36-84% yield by the Prins reaction. A strongly electron-donating methoxy substituent at either the ortho or para position of the styrene did not give the expected 3-chloro-3-arylpropanols ...
Tanyeli, Cihangir (Informa UK Limited, 1989-01-01)
Some phenolic biphenyl compounds have been synthesised via the annulation reactions of 4-methoxy-2- pyrone with various active methyl compounds.
Metal triflates-catalyzed conjugate addition of homochiral Pyrroles to alpha,beta-unsaturated esters
Unaleroglu, C; Temelli, B; Demir, Ayhan Sıtkı (Georg Thieme Verlag KG, 2004-10-18)
The Friedel-Crafts reaction of homochiral pyrrole derivatives with alpha,beta-unsaturated esters catalyzed by metal triflates furnished conjugate addition products. The best yields were obtained by using yttrium triflate and methyl 4-phenyl-2-oxobut-3-enoate (2a). The addition worked regioselectively at C-5 of pyrrole. The diastereoisomers were separated by column chromatography.
Naphthazarin-Polycyclic Conjugated Hydrocarbons and Iptycenes
Dengiz, Çağatay; GUTIERREZ, Gregory D.; SWAGER, Timothy M. (American Chemical Society (ACS), 2017-07-21)
The synthesis of a set of naphthazarin-containing polycyclic conjugated hydrocarbons is described herein. Sequential Diels-Alder reactions on a tautomerized naphthazarin core were employed to access the final conjugated systems. Complete conjugation across the backbone can be achieved through complexation with BF2, as observed by (HNMR)-H-1 analysis and UV/vis spectroscopy. Precise synthetic control over the degree of oxidation of naphthazarin quinone Diels-Alder adduct 10 is additionally demonstrated and e...
Citation Formats
M. Balcı, “Acyl Azides: Versatile Compounds in the Synthesis of Various Heterocycles,” SYNTHESIS-STUTTGART, pp. 1373–1401, 2018, Accessed: 00, 2020. [Online]. Available: