Organic Chemistry Portal
Organic Chemistry Highlights

Monday, October 28, 2019
Douglass F. Taber
University of Delaware

C-H Functionalization: The Reisman Synthesis of Rumphellaone A

Mathieu Lesieur and Patrick Pasau of UCB Biopharma and Steven V. Ley of the University of Cambridge developed a flow protocol with 2 for the selective hydroxylation of 1 to 3 (Chem. Eur. J. 2019, 25, 1203. DOI: 10.1002/chem.201805657). M. Christina White of the University of Illinois observed similar inductive deactivation in the oxidation of 4, leading to the cyclopentanone 5 (Nature Chem. 2019, 11, 213. DOI: 10.1038/s41557-018-0175-8). Darren J. Dixon of the University of Oxford used the dithiane of 6 to direct coupling with 7, leading to 8 (Chem. Sci. 2019, 10, 3733. DOI: 10.1039/C8SC05225E). Tomislav Rovis of Columbia University coupled 9 with 10 to give the branched product 11 (J. Am. Chem. Soc. 2019, 141, 2268. DOI: 10.1021/jacs.9b00237). Frank Glorius of the Westfälische Wilhelms-Universität Münster observed parallel results (Angew. Chem. Int. Ed. 2019, 58, 7117. DOI: 10.1002/anie.201901733).

Uttam K. Tambar of the University of Texas Southwest Medical Center achieved selective allylation of 12 with 13, leading to 14 (ACS Catal. 2019, 9, 4627. DOI: 10.1021/acscatal.9b00563). Vladimir Gevorgyan of the University of Illinois at Chicago devised the coupling of 15 with 16 to give, after reduction, the alcohol 17 (Angew. Chem. Int. Ed. 2019, 58, 1794. DOI: 10.1002/anie.201812398). David B. C. Martin, now at the University of Iowa, observed that the hybridization of the methine adamantane sites are such that 18 could be coupled with 19 to give 20 (ACS Catal. 2019, 9, 5708. DOI: 10.1021/acscatal.9b01394). Xiao-Feng Wu of the Universität Rostock carbonylated 21, leading to 22 (Chem. Commun. 2019, 55, 4655. DOI: 10.1039/C9CC02112D).

David A. Nagib of Ohio State University arylated 23 with 24, then cyclized that product to the pyrrolidine 25 (Chem. Sci. 2019, 10, 1207. DOI: 10.1039/C8SC04366C). Eric Meggers of the Philipps-Universität Marburg cyclized 26 to 27 in high ee (Chem. Sci. 2019, 10, 3202. DOI: 10.1039/C9SC00054B). Daniel Solé of the Universitat de Barcelona and Israel Fernández of the Universidad Complutense de Madrid used a Grubbs catalyst to cyclize 28 to 29 (Chem. Commun. 2019, 55, 1160. DOI: 10.1039/C8CC09089K). Remigiusz Żurawiński of the Polish Academy of Sciences showed that cyclization of 30 could be followed by β elimination, leading to 31 (Eur. J. Org. Chem. 2019, 2612. DOI: 10.1002/ejoc.201900102).

Rumphellaone A (35), isolated from the gorgonian coral Rumphella antipathies, shows interesting anti-proliferative activity. En route to 35, Sarah E. Reisman of CalTech prepared 34 by coupling 32 with 33 (Chem. Sci. 2019, 10, 2315. DOI: 10.1039/C8SC05444D).

D. F. Taber, Org. Chem. Highlights 2019, October 28.