Unified Total Syntheses of Benzenoid Cephalotane Norditerpenoids

An organic chemistry minilecture on the Unified Total Syntheses of Benzenoid Cephalotane-Type Norditerpenoids: Cephanolides and Ceforalides by Goh Sennari, Kristen E. Gardner, Stefan Wiesler, Maximilian Haider, Alina Eggert and Richmond Sarpong*. It features a lot of interesting reactions such as a thianthrenation, a Ru-catalysed photo oxidation and an Ir-catalysed protodeborylation. SUPPORT THE CHANNEL ON PATREON: NMR Spectroscopy in music: J. New Music Res. 2021, 50:5, 487-501 Socials: References: J. Am. Chem. Soc. 2022, 144, 31, 14042–14046 (This work) Phytochemistry 2021, 192, No. 112939 (Review of cephalotane diterpenoids) J. Org. Chem. 1994, 59, 20, 6095–6097 Flouride accelerated Suzuki coupling) Chem. Eur. J. 2013,19, 10082 – 10093 (Flouride accelerated Suzuki coupling) Tetrahedron Lett. 1984, 25, 1953−1956. (Suarez oxidation) Nature 2019, 567, 223−228. (Ritter thianthrenylation) Chem. Sci. 2019, 10, 6210−6214 (Protodeborylation) J. Org. Chem. 2001, 66, 23, 7741–7744 (Indium promoted deoxygenation) Nature 2013, 499, 192−196. (PPO Oxidation) Org. Lett. 2015, 17, 19, 4866–4869 (Pd- catalyzed carbonylation) (J. Org. Chem. 2020, 85, 20, 12901–12911 (Thiourea-mediated bromination) Chem. Sci., 2017,8, 7180-7185 (Photo oxidation) Org. Biomol. Chem., 2018,16, 2324-2329 (Iodine-mediated dearomatization) 0:00 Introduction 0:16 Unified Total Syntheses of Benzenoid Cephalotane-Type Norditerpenoids: Cephanolides and Ceforalides 1:10 Strategy 1:55 Suzuki-Miyaura Coupling 2:25 Diels-Alder Cycloaddition 3:00 Methyl-Borylation/ Oxidation 3:34 DMP Oxidation 3:53 Reduction 4:04 Suarez Oxidation 4:50 Barton-McCombie Deoxygenation 5:44 Thianthrenation 6:44 Protodeboronation 7:19 Deprotection 8:28 Benzylic Oxidation 8:49 Methoxycarbonylation 9:55 Jones Oxidation 10:31 Bromination 11:14 Dehalogenation 11:48 Photo-Oxidation 12:32 Oxidative Cyclization 13:39 Oxidative Dearomatization