Screening of simple carbohydrates as a renewable organocatalyst for the efficient construction of 1, 3-benzoxazine scaffold. (December 2021)

• Record Type: Journal Article
• Authors: Yıldırım, Ayhan; Kaya, Yunus; Göker, Mustafa
• Is Part Of: Carbohydrate research. Volume 510(2021)
• Publication Date: 2021-12
• Subjects: 1, 3-Benzoxazines -- Carbohydrates -- DFT studies -- Organocatalysis -- Sustainable chemistry; Carbohydrates -- Periodicals; Chemistry, Organic -- Periodicals; Biochemistry -- Periodicals; Carbohydrates -- Periodicals; Chimie organique -- Périodiques; Glucides -- Périodiques; Biochemistry; Carbohydrates; Chemistry, Organic; Periodicals; Electronic journals; 507.78
• DOI: 10.1016/j.carres.2021.108458
• Languages: English
• ISSNs: 0008-6215

Abstract

Abstract: A convenient protocol for the two component preparation of 1, 3-benzoxazines by using several protected and unprotected carbohydrate molecules as organocatalysts have been developed which is broadly applicable to condensation reaction between variety of Mannich bases and paraformaldehyde. This study revealed that fructose have much higher catalytic activity than the other carbohydrates and can be an alternative to metal-containing catalysts as a green renewable organocatalyst for efficient and rapid construction of 1, 3-benzoxazine skeleton. In this context, 21 benzoxazine compounds were successfully synthesized and spectral characterizations of these compounds were carried out by spectroscopic methods and elemental analysis. Furthermore, density functional theory (DFT) calculations have been performed to study the detailed mechanism of organocatalyst assisted synthesis of the benzoxazine monomers. The results obtained from these calculations showed that the more realistic reaction pathway involves formation of a phenolate based intermediate which loses a water molecule to form benzenaminium ion. Subsequently, this ion provides the formation of the corresponding benzoxazines with good yields through the intramolecular ring closure step. Graphical abstract: Image 1 Highlights: Renewable and inexpensive bio-based organocatalyst. Very short reaction times. Easy work-up and good yield of the benzoxazine monomers.