Benzoxaborole Catalyst for Site‐Selective Modification of Polyols. Issue 11 (3rd February 2020)

• Record Type: Journal Article
• Authors: Kusano, Shuhei; Miyamoto, Shoto; Matsuoka, Aki; Yamada, Yuji; Ishikawa, Ryuta; Hayashida, Osamu
• Is Part Of: European journal of organic chemistry. Issue 11(2020)
• Page Start: 1598
• Page End: 1602
• Publication Date: 2020-02-03
• Subjects: Benzoxaborole -- Polyols -- cis‐1, 2‐Diols -- Site‐selective modification -- Glycosylation; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201901749
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : The site‐selective modification of polyols bearing several hydroxyl groups without the use of protecting groups remains a significant challenge in synthetic chemistry. To address this problem, novel benzoxaborole derivatives were designed as efficient catalysts for the highly site‐selective and protecting‐group‐free modification of polyols. To identify the effective substituent groups enhancing the catalytic activity and selectivity, a series of benzoxaborole catalysts 1a –k were synthesized. In‐depth analysis for the substituent effect revealed that 1i –k, bearing multiple electron‐withdrawing fluoro‐ and trifluoromethyl groups, exhibited the greatest catalytic activity and selectivity. Moreover, 1i ‐catalyzed benzoylation, tosylation, benzylation, and glycosylation of various cis‐1, 2‐diol derivatives proceeded with good yield and site‐selective manner. Abstract : Novel benzoxaborole derivatives were designed as efficient catalysts for the highly site‐selective and protecting‐group‐free modification of polyols, such as carbohydrate. Additionally, the benzoxaborole catalyst could tolerate diverse modifications of polyols, including acylation, sulfonylation, alkylation, and glycosylation.