Organic Chemistry Portal
Organic Chemistry Highlights

Monday, June 27, 2022
Douglass F. Taber
University of Delaware

Functional Group Interconversion: The Wang Synthesis of Spirojatamol

Daniele Leonori, now at RWTH Aachen University, employed visible light to promote the Co-catalyzed elimination of the primary bromide 1 to the alkene 2 (J. Am. Chem. Soc. 2021, 143, 14806. DOI: 10.1021/jacs.1c06768). Yan Xu and Guangbin Dong of the University of Chicago used the hydrazonamide 4 to mediate the deacylative conversion of the ketone 3 to the alkene 5 (J. Am. Chem. Soc. 2021, 143, 20042. DOI: 10.1021/jacs.1c09587). Jung-Woo Park of KAIST established conditions for converting the internal alkyne 6 to the branched terminal alkenyl silane 7 (ACS Catal. 2021, 11, 12777. DOI: 10.1021/acscatal.1c03769). Gerhard Hilt of the Universität Oldenburg devised electrolytic conditions for the conversion of cyclohexene 8 to the cis 1,2-dichlorocyclohexane 9 (Chem. Eur. J. 2021, 27, 17341. DOI: 10.1002/chem.202103316).

Masahiro Noji and Toshikatsu Takanami of Meiji Pharmaceutical University optimized the rearrangement of the epoxide 10 to the allylic alcohol 11 (Chem. Commun. 2021, 57, 7104. DOI: 10.1039/D1CC02840E). Fabio Julía, also of the University of Manchester, and Professor Leonori effected the conversion of the secondary iodide 12 to the primary amine 13 (Nature Catal. 2021, 4, 623. DOI: 10.1038/s41929-021-00652-8). Tao Wang and Junkai Fu of Jiangxi Normal University used 15 to selectively demethylate the tertiary amine 14, leading to the amide 16 (Synlett 2021, 32, 1642. DOI: 10.1055/a-1517-5895). Kevin Lam of the University of Greenwich prepared the isonitrile 18 by electrolytic oxidation of the aminotetrazole 17 (Org. Lett. 2021, 23, 9371. DOI: 10.1021/acs.orglett.1c03475).

Qiang Tang of Chongqing Medical University found that sulfuryl chloride smoothly converted the β-keto ester 19 to the 2,2-dichloro ketone 20 (Tetrahedron Lett. 2021, 81, 153335. DOI: 10.1016/j.tetlet.2021.153335). John E. Moses of Cold Spring Harbor Laboratory used a catalytic aminium cation radical to hydrate the eneyne 21 to the enone 22 (Chem. Commun. 2021, 57, 6991. DOI: 10.1039/D1CC02257A). Professor Dong used a modified Catellani protocol with the norbornene amide 24 and the N-acyloxy morpholine 25 to convert the enol triflate 23 to the ketone 26, a net 1,2-carbonyl transposition (Science 2021, 374, 734. DOI: 10.1126/science.abl7854). D. Srinivasa Reddy of CSIR-Indian Institute of Integrative Medicine showed that 1,3-transposition of the E-enone 27 led cleanly to the Z-enone 28 (Org. Lett. 2021, 23, 6642. DOI: 10.1021/acs.orglett.1c02173).

The sesquiterpene spirojatamol (31) was isolated from the roots of Nardostachys jatamansi, a flowering plant of the valerian family that grows in the Himalayas. In the course of a synthesis of 31, Shao-Hua Wang of Lanzhou University achieved remarkable regioselectivity in the conversion of the ketone 29 to the alkene 30 (Tetrahedron Lett. 2021, 85, 153291. DOI: 10.1016/j.tetlet.2021.153291).

D. F. Taber, Org. Chem. Highlights 2022, June 27.