Enantioselective Synthesis of Arene cis‐Dihydrodiols from 2‐Pyrones

• Published in: Angewandte Chemie International Edition Vol. 58; no. 41; pp. 14562 - 14567
• Main Authors: Liang, Xiao‐Wei, Zhao, Yunlong, Si, Xu‐Ge, Xu, Meng‐Meng, Tan, Jia‐Hao, Zhang, Zhi‐Mao, Zheng, Cheng‐Gong, Zheng, Chao, Cai, Quan
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 07.10.2019; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: asymmetric catalysis; Asymmetry; Carbon dioxide; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Diels–Alder reaction; dihydrodiols; Enantiomers; Extrusion; Organic chemistry; Physical Sciences; retro-Diels–Alder reactions; Science & Technology; total synthesis; Ytterbium; MICROBIAL OXIDATION; ASYMMETRIC-SYNTHESIS; DIELS-ALDER REACTIONS; OXYGENATED AROMATICS; ELECTRONICALLY MATCHED 2-PYRONES; asymmetric catalysis; METHYL COUMALATE; AROMATIC-HYDROCARBONS; retro-Diels-Alder reactions; CHEMOENZYMATIC TOTAL-SYNTHESIS; Diels-Alder reaction; total synthesis; ENZYMATIC DIHYDROXYLATION; OXIDATIVE-DEGRADATION; dihydrodiols
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201908284

An enantioselective chemical synthesis of arene cis‐dihydrodiols has been realized from 2‐pyrones through sequential ytterbium‐catalyzed asymmetric inverse‐electron‐demand Diels–Alder (IEDDA) reaction of 2‐pyrones and retro‐Diels–Alder extrusion of CO2. By using this strategy, a series of substituted arene cis‐dihydrodiols can be obtained efficiently with high enantioselectivity (>99 % ee in many cases). Based on this strategy, efficient and concise asymmetric total syntheses of (+)‐MK7607 and 1‐epi‐(+)‐MK7607 were accomplished. An enantioselective chemical synthesis of arene cis‐dihydrodiols from 2‐pyrones through sequential ytterbium‐catalyzed asymmetric inverse‐electron‐demand Diels–Alder (IEDDA) reaction of 2‐pyrones and retro‐Diels–Alder extrusion of CO2 is reported. This method provides a powerful chemical method for the enatioselective synthesis of arene cis‐dihydrodiols as a reliable alternative to traditional enzymatic catalysis.