Organic Chemistry Portal
Organic Chemistry Highlights

Monday, June 17, 2013
Douglass F. Taber
University of Delaware

Substituted Benzenes: The Subba Reddy Synthesis of 7-Desmethoxyfusarentin

Andrey P. Antonchick of the Max-Planck-Institut Dortmund devised (Org. Lett. 2012, 14, 5518. DOI: 10.1021/ol302607y) a protocol for the direct amination of an arene 1 to give the amide 3. Douglas A. Klumpp of Northern Illinois University showed (Tetrahedron Lett. 2012, 53, 4779. DOI: 10.1016/j.tetlet.2012.06.135) that under strong acid conditions, an arene 4 could be carboxylated to give the amide 6. Eiji Tayamaof Niigata University coupled (Tetrahedron Lett. 2012, 53, 5159. DOI: 10.1016/j.tetlet.2012.07.070) an arene 7 with the α-diazo ester 8 to give 9. Guy C. Lloyd-Jones and Christopher A. Russell of the University of Bristol activated (Science 2012, 337, 1644. DOI: 10.1126/science.1225709) the aryl silane 11 to give an intermediate that coupled with the arene 10 to give 12.

Ram A. Vishwakarma and Sandip P. Bharate of the Indian Institute of Integrative Medicine effected (Tetrahedron Lett. 2012, 53, 5958. DOI: 10.1016/j.tetlet.2012.08.121) ipso nitration of an areneboronic acid 13 to give 14. Stephen L. Buchwald of MIT coupled (J. Am. Chem. Soc. 2012, 134, 11132. DOI: 10.1021/ja305212v) sodium isocyanate with the aryl chloride 15 (aryl triflates also worked well) to give the isocyanate 16, that could be coupled with phenol to give the carbamate, or carried on to the unsymmetrical urea.

Zhengwu Shen of the Shanghai University of Traditional Chinese Medicine used (Org. Lett. 2012, 14, 3644. DOI: 10.1021/ol3014914) ethyl cyanoacetate 18 as the donor for the conversion of the aryl bromide 17 to the nitrile 19. Kuo Chu Hwang of the National Tsig Hua University showed (Adv. Synth. Catal. 2012, 354, 3421. DOI: 10.1002/adsc.201200683) that under the stimulation of blue LED light, the Castro-Stephens coupling of 20 with 21 proceeded efficiently at room temperature.

Lutz Ackermann of the Georg-August-Universitat Gottingen employed (Org. Lett. 2012, 14, 4210. DOI: 10.1021/ol3018819) a Ru catalyst to oxidize the amide 23 to the phenol 24. Both Prof. Ackermann (Org. Lett. 2012, 14, 6206. DOI: 10.1021/ol302956s) and Guangbin Dong of the University of Texas (Angew. Chem. Int. Ed. 2012, 51, 13075. DOI: 10.1002/anie.201207479) described related work on the ortho hydroxylation of aryl ketones. George A. Kraus of Iowa State University rearranged (Tetrahedron Lett. 2012, 53, 7072. DOI: 10.1016/j.tetlet.2012.10.058) the aryl benzyl ether 25 to the phenol 26. The synthetic utility of the triazene 27 was demonstrated (Angew. Chem. Int. Ed. 2012, 51, 7242. DOI: 10.1002/anie.201203230) by Yong Huang of the Shenzen Graduate School of Peking University. The triazene effectively mediated ortho C-H functionalization to give 29, then was carried on, inter alia, to the iodide 30.

The dihydroisocoumarin 7-Desmethoxyfusarentin (34) was isolated from the insect pathogenic fungus Ophiocordyceps communis. B. V. Subba Reddy prepared (Tetrahedron Lett. 2012, 53, 4051. DOI: 10.1016/j.tetlet.2012.05.059) the arene of 33 by the Alder-Rickert reaction of 31 with the Birch reduction product 32.

D. F. Taber, Org. Chem. Highlights 2013, June 17.