Organic Chemistry Portal
Organic Chemistry Highlights

Monday, September 30, 2019
Douglass F. Taber
University of Delaware

Reactions of Alkenes: The Qin Synthesis of Arcutinine

Yusuyuki Ura of Nara Women's University combined 2 with the alkene 1, leading to the protected aldehyde 2 (J. Org. Chem. 2019, 84, 3093. DOI: 10.1021/acs.joc.8b02919). Rong Zhu of Peking University added 5 to 4 to give the Markovnikov ester 6 (J. Am. Chem. Soc. 2019, 141, 7250. DOI: 10.1021/jacs.9b01857). Silas P. Cook of Indiana University reported the formation of Markovnikov ethers and amines (Org. Lett. 2019, 21, 1547. DOI: 10.1021/acs.orglett.9b00427). By anti-Markovnikov azidation, Wei Yu of Lanzhou University converted 7 to 8 (Chem. Eur. J. 2019, 25, 3510. DOI: 10.1002/chem.201806371). Hao Xu of Georgia State University described related results (J. Am. Chem. Soc. 2019, 141, 9415. DOI: 10.1021/jacs.9b04381). Amir H. Hoveyda of Boston College showed that including HB(pin) (11) in the cross metathesis of 9 with 10 enhanced the preparation of the alkenyl chloride 12 (Angew. Chem. Int. Ed. 2019, 58, 5365. DOI: 10.1002/anie.201901132).

Yuanhong Liu of the Shanghai Institute of Organic Chemistry showed that Zn(CN)2 could be used for the hydrocyanation of 13 to 14 (Org. Chem. Front. 2019, 6, 2037. DOI: 10.1039/C9QO00396G). Michael Schnürch of TU Wien assembled 17 by adding 16 to 15 (Org. Biomol. Chem. 2019, 17, 4024. DOI: 10.1039/C9OB00243J). Xin Xu of Soochow University reported a related transformation (Org. Biomol. Chem. 2019, 17, 2013. DOI: 10.1039/C8OB02657B). Frank Glorius of the Westfälische Wilhelms-Universität Münster effected oxidative allylation of 18 with 1, leading to 19 (ACS Catal. 2019, 9, 1253. DOI: 10.1021/acscatal.8b04677). Ryan A. Shenvi of Scripps-La Jolla demonstrated that the carboxylate of 20 directed the regioselectivity of the Heck addition of 21 to 20 to give 22 (Angew. Chem. Int. Ed. 2019, 58, 2371. DOI: 10.1002/anie.201813233).

Yunhe Lv of Northeast Normal University used a Cu catalyst to mediate the preparation of 25 by the addition of 24 to 23 (Chem. Commun. 2019, 55, 4821. DOI: 10.1039/C9CC01988J). Hongli Bao of the Fujian Institute of Research on the Structure of Matter used an iron catalyst to effect the addition of 27 to 26, leading to 28 (Nature Commun. 2019, 10, 122. DOI: 10.1038/s41467-018-07985-2). Armido Studer, also of the Westfälische Wilhelms-Universität, prepared 32 by the addition of 31 to 29 in the presence of 30 (Chem. Eur. J. 2019, 25, 516. DOI: 10.1002/chem.201805490). Gebhard Haberhauer of the Universität Duisburg-Essen described alkene alkynylation with complementary regioselectivity (J. Org. Chem. 2019, 84, 8210. DOI: 10.1021/acs.joc.9b01371). James P. Morken, also of Boston College, assembled the β-hydroxyketone 35 by the boron-mediated coupling of 33 with vinyl lithium and then 34 (Angew. Chem. Int. Ed. 2019, 58, 6654. DOI: 10.1002/anie.201901927).

Arcutinine (38) was isolated from the aerial parts of the flowering shrub Aconitum fischeri var. arcuatum (Wolf's bane). En route to 38, Yong Qin of the West China School of Pharmacy effected the equilbrating isomerization of 36 to 37, setting the stage for Pd-catalyzed aza-Wacker cyclization followed by intramolecular Diels-Alder cycloaddition (J. Am. Chem. Soc. 2019, 141, 9712. DOI: 10.1021/jacs.9b04847).

D. F. Taber, Org. Chem. Highlights 2019, September 30.