Organic Chemistry Portal
Organic Chemistry Highlights

Monday, May 29, 2017
Douglass F. Taber
University of Delaware

Interconversion of Organic Functional Groups

David B. Collum of Cornell University developed (J. Org. Chem. 2016, 81, 11312. DOI: 10.1021/acs.joc.6b02287) sodium diisopropylamide as a useful reagent for many base-mediated transformations, including the conversion of 1 to 2. Seth B. Herzon of Yale University devised (J. Org. Chem. 2016, 81, 8673. DOI: 10.1021/acs.joc.6b01709) oxidative conditions for the net hydrolysis of an alkenyl halide 3 to the ketone 4. Alkenyl sulfides and alkenyl silanes were also converted to ketones. Graham E. Dobereiner of Temple University observed (Adv. Synth. Catal. 2016, 358, 4106. DOI: 10.1002/adsc.201601013) substantial regioselectivity in the Au-mediated hydration of the alkyne 5 to the ketone 6. Janez Kosmrlj of the University of Ljubljana and Tsuyoshi Taniguchi of Kanazawa University described (Chem. Sci. 2016, 7, 5148. DOI: 10.1039/C6SC00308G) in more detail the Mitsunobu conversion of 7 to 9 using catalytic 8, but cast doubt (Org. Lett. 2016, 18, 4036. DOI: 10.1021/acs.orglett.6b01894) on the previously-described (Functional Group Interconversion: The Danishefsky Synthesis of Granulocyte Colony-Stimulating Factor 2016, May 30) "fully catalytic" Mitsunobu reaction.

Belén Martín-Matute of Stockholm University optimized (Chem. Eur. J. 2016, 22, 15659. DOI: 10.1002/chem.201603825) the Ir-mediated conversion of 10 to 11. Clément Mazet of the University of Geneva demonstrated (J. Am. Chem. Soc. 2016, 138, 10344. DOI: 10.1021/jacs.6b06390) that 12 was isomerized smoothly to 13, the Pd-mediated bond migration having successfully traversed the alkylated stereogenic center.

Petri M. Pihko of the University of Jyväskylä effected (Synlett 2016, 27, 1649. DOI: 10.1055/s-0035-1561633) the net reductive hydration of the enal 14 to the diol 15. John F. Hartwig of the University of California, Berkeley established (ACS Central Sci. 2016, 2, 647. DOI: 10.1021/acscentsci.6b00187) conditions for the selective coupling of the tertiary bromide of 16 with 17 to give 18.

Liang-Nian He of Nankai University showed (Chem. Eur. J. 2016, 22, 16489. DOI: 10.1002/chem.201603688) that CO2 could be used to methylate the amine 19, leading to 20. Peipei Sun of Nanjing Normal University opened (Org. Biomol. Chem. 2016, 14, 7018. DOI: 10.1039/C6OB01208F) the amine 21 with TsCl and a copper catalyst to give 22. Hiroaki Tsuji and Hisashi Yamamoto of Chubu University developed (J. Am. Chem. Soc. 2016, 138, 14218. DOI: 10.1021/jacs.6b09482) Ta ethoxide as a specific catalyst for the amination of the β-hydroxy ester of 23 with 24 to give the amide 25. Junfeng Zhao of Jiangxi Normal University demonstrated (J. Am. Chem. Soc. 2016, 138, 13135. DOI: 10.1021/jacs.6b07230) that using 28 as the coupling reagent, 29 could be prepared from 26 and 27 with no observable epimerization.

Several years ago, we observed that a bromide such as 31 prepared from 30 using Br2/Ph3P would not form the Grignard reagent. After bulb-to-bulb distillation of 31, the Grignard formed readily. We did not originate this - does anyone have the reference?

D. F. Taber, Org. Chem. Highlights 2017, May 29.