tert‐Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis

Abstract

The upsurge interesti nt he development of efficient methodologies for the constructiono fn itrogen-containing frameworks via the use of expedient reagents have been creating ar enaissance in contemporary organic chemistry.I nt his perspective, tertbutyl nitrite (TBN) is an emerging building block. Due to its uniques tructuralf eatures, it shows differential reactivity under different reaction conditions. These diverse reactivities have resulted in the construction of ad iverse array of complex N-containing molecules. The primary objective of the presentr eview is to bring the latest findings of TBN in terms of its applications in reactions (oxidation, diazotization, nitrosation, nitration, oximation, N-synthon, and miscellaneous reactions) into the limelight.F or simplicity and brevity,r eactions in each section are explained with the mechanism of formation and selected examples are given.Scheme1.Differential reactivity of TBN. 4455 MinireviewScheme4.Visible-light-promoted synthesis of selenide ethers.Scheme5.Proposed mechanism for visible-light-promoted synthesis of selenide ethers.Scheme6.TBN-mediated synthesis of selenide ethers.Scheme7.Metal-free synthesis of 4-carbonylquinolines.Scheme8.Proposed mechanism for synthesis of 4-carbonylquinolines.Scheme9.TBN-mediated demethylative borylation of methylarenes.Scheme10. Plausible mechanism for demethylative borylation of methylarenes.Scheme11. Trifluoromethylation of various aromatic amine substrates.Scheme12. Copper-catalyzed isoperfluoropropylation of anilines.Scheme13. Plausible mechanism for Cu-catalyzed isoperfluoropropylation of anilines.Scheme14. TBN-mediateddiazotizative allylation of aromatic amines.Scheme15. Oxidativecyanomethylationo fa lkenes via CÀHb ond activation.Scheme16. TBN-mediatedand Cu-catalyzedsynthesis of thioether.

Metal‐free Synthesis of β‐Nitrostyrenes via DDQ‐Catalyzed Nitration

“…Accordingly, we envisioned that DDQ, as an essential oxidant, could be involved in either a hydrogen atom transfer process or a single electron transfer process in the nitration reaction of styrenes with TBN as shown in Scheme 2. In this concept, TBN serves as a crucial nitrating agent, 10 of which homolytic cleavage by any hydrogen source might accelerate generation of NO radical at room temperature. Thus, the use of DDQ would be suitable for development of a mild reaction condition as well as our proposed nitration process 11 …”

Unravelling the mechanism of cobalt-catalysed remote C–H nitration of 8-aminoquinolinamides and expansion of substrate scope towards 1-naphthylpicolinamide

“…14 Resulting from the rich aforementioned chemistry of Co, in 2016 some of us reported on the unexpected remote nitration of 8-aminoquinolinamide scaffold using tert-butyl nitrite (TBN) as nitro source (Scheme 1b). 15,16 This was the rst time that Co had been observed to display this type of reactivity. Since this report, others have also been attracted to the potential of this novel potential for Co in the eld of C-H functionalisation (Scheme 1c and d).…”

Real Metal-Free C–H Arylation of (Hetero)arenes: The Radical Way

“…In this regard, the possibility of obtaining biaryls directly from anilines through their conversion in situ into arenediazonium salts represents a better, secure and environmentally benign approach to handle potentially thermo-and shock-sensitive arenediazonium salts. 24 According to these considerations, in 2017 Patel and coworkers published an interesting study on the Gomberg-Bachmann arylation of five-membered heteroarenes with arenediazonium salts generated in situ from t-BuONO 25 in MeCN at room temperature. 26 Using 4-nitroaniline and furan as model reaction partners, the authors isolated the expected 2-(4-nitrophenyl)furan in 68% yield.…”