Fine bubble technology for the green synthesis of fairy chemicals

• Published in: Organic & biomolecular chemistry Vol. 22; no. 17; pp. 3396 - 344
• Main Authors: Manna, Arun Kumar, Doi, Mizuki, Matsuo, Keiya, Sakurai, Hiroto, Subrahmanyam, Ch, Sato, Kohei, Narumi, Tetsuo, Mase, Nobuyuki
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 01.05.2024
• Subjects: Acetates; Acetic acid; Bubbles; Chemical reactions; Chemical synthesis; Hormones; Imidazole; Metabolic pathways; New class; Plant growth; Plant growth substances; Plants; Purines
• ISSN: 1477-0520; 1477-0539
• DOI: 10.1039/d4ob00237g

Fairy chemicals (FCs), such as 2-azahypoxanthine (AHX), are a potential new class of plant hormones that are naturally present in plants and produced via a novel purine metabolic pathway. FCs support plant resilience against various stresses and regulate plant growth. In this study, we developed a four-step method for synthesising AHX from 2-cyanoacetamide, achieving a good yield. Oxime was obtained from 2-cyanoacetamide via the oximation reaction. Cascade-type one-pot selective Pt/C-catalysed reduction of oxime, followed by a coupling reaction with formamidine acetate, yielded intermediate 5-amino-1 H -imidazole-4-carboxamide (AICA). For the synthesis of AICA from oxime, we used modern fine bubble technology, affording AICA in 69% yield. Subsequently, we synthesised 4-diazo-4 H -imidazole-5-carboxamide (DICA) from AICA via the diazotisation reaction. Notably, the synthesis of DICA from AICA was achieved, and the stability of previously known less stable DICA in the solid state was confirmed. Finally, PhI(OAc) 2 (0.5 mol%) catalysed the intramolecular cyclisation of DICA in the green solvent water to yield AHX (overall yield of 47%). This study's innovative techniques and substantial discoveries highlight its potential influence and significance in FC science, thereby establishing a new standard for subsequent research. Fairy chemicals (FCs) such as 2-azahypoxanthine (AHX), isolated from naturally occurring sources, are potential phytohormones in plants and efficiently synthesized by fine bubble technology consisting of micro- to nano-sized bubbles.