Synthesis of Aldehydes by Organocatalytic Formylation Reactions of Boronic Acids with Glyoxylic Acid

• Published in: Angewandte Chemie International Edition Vol. 56; no. 28; pp. 8201 - 8205
• Main Authors: Huang, He, Yu, Chenguang, Li, Xiangmin, Zhang, Yongqiang, Zhang, Yueteng, Chen, Xiaobei, Mariano, Patrick S., Xie, Hexin, Wang, Wei
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 03.07.2017; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Acids; Aldehydes; Amines; Amino acids; arenes; Aromatic compounds; boron; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Forming; formylation; Functional groups; Glyoxylic acid; organocatalysis; Physical Sciences; Science & Technology; synthetic methods; CASCADE REACTIONS; ALLYLIC RADICALS; formylation; CATALYZED FORMYLATION; BROMIDES; ARYLBORONIC ACIDS; INDOLES; CIS-TRANS-ISOMERIZATION; organocatalysis; VISIBLE-LIGHT; arenes; CARBON-MONOXIDE; ARYL HALIDES; boron; synthetic methods
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201703127

Reported herein is a conceptually novel organocatalytic strategy for the formylation of boronic acids. New reactivity is engineered into the α‐amino‐acid‐forming Petasis reaction occurring between aryl boronic acids, amines, and glyoxylic acids to prepare aldehydes. The operational simplicity of the process and its ability to generate structurally diverse and valued aryl, heteroaryl, and α,β‐unsaturated aldehydes containing a wide array of functional groups, demonstrates the practical utility of the new synthetic strategy. All functional: A conceptually novel organocatalytic strategy for synthesis of aldehydes is reported. A new reactivity is engineered into the α‐amino‐acid‐forming Petasis reaction to create an unprecedented amine‐promoted formylation of boronic acids using glyoxylic acid as a formylation reagent. Both aryl and alkenyl boronic acids, with a variety of functional groups, can serve as substrates.