In particular, homogeneous metal-catalyzed aerobic oxidation of benzylic methylenes has attracted much attention.
Garazi Urgoitia, Raul SanMartin, María Teresa Herrero, Esther Domínguez 2018, 'Recent Advances in Homogeneous Metal-Catalyzed Aerobic C–H Oxidation of Benzylic Compounds',Catalystshttps://www.mdpi.com/2073-4344/8/12/640. Retrieved from DOAJ CC BY 4.0 (https://creativecommons.org/licenses/by-sa/4.0/legalcode)
Branched, cyclic, allylic and benzylic alkylamino/arylamino groups were introduced into the quinone moiety.
Jeremić Marko, Dinić Jelena, Pešić Milica, Stepanović Marija, Novaković Irena, ŠeganDejan, Sladić Dušan 2018, 'Alkylamino and aralkylamino derivatives of avarone and its mimetic as selective agentsagainst non-small cell lung cancer cells, their antibacterial and antifungal potential',Journal of the Serbian Chemical Societyhttp://www.doiserbia.nb.rs/img/doi/0352-5139/2018/0352-51391800062J.pdf. Retrieved from DOAJ CC BY 4.0 (https://creativecommons.org/licenses/by-sa/4.0/legalcode)
A subsequent 1,3-proton shift of the benzylic proton of 4 forms 3.
Akari Ikeda, Masaaki Omote, Shiho Nomura, Miyuu Tanaka, Atsushi Tarui, Kazuyuki Sato,Akira Ando 2013, 'Oxidative 3,3,3-trifluoropropylation of arylaldehydes', Beilstein Journal of Organic Chemistryhttps://doi.org/10.3762/bjoc.9.279. Retrieved from DOAJ CC BY 4.0 (https://creativecommons.org/licenses/by-sa/4.0/legalcode)
The benzylic iodide intermediate then solvolyzes to yield the product ester.
Kelsey B. LaMartina, Haley K. Kuck, Linda S. Oglesbee, Asma Al-Odaini, Nicholas C.Boaz 2019, 'Selective benzylic C–H monooxygenation mediated by iodine oxides', Beilstein Journal of Organic Chemistryhttps://doi.org/10.3762/bjoc.15.55. Retrieved from DOAJ CC BY 4.0 (https://creativecommons.org/licenses/by-sa/4.0/legalcode)
Benzylic pinacols rearrange under these conditions, while aliphatic pinacols do not react.
Ebrahim Kianmehr, Parviz Rashidi-Ranjbar 2001, 'Facile and Fast Pinacol Rearrangement by AlCl3 in the Solid State', Moleculeshttp://www.mdpi.com/1420-3049/6/5/442/. Retrieved from DOAJ CC BY 4.0 (https://creativecommons.org/licenses/by-sa/4.0/legalcode)
It was also interesting that the lipase-catalyzed acylation couldn't be influenced by the benzylic alcohol in gastrodin.
Rongling Yang, Xueming Liu, Zhiyi Chen, Chunying Yang, Yaosheng Lin, Siyuan Wang 2014, 'Highly Efficient and Enzymatic Regioselective Undecylenoylation of Gastrodin in 2-Methyltetrahydrofuran-ContainingSystems', PLoS ONE10.1371/journal.pone.0110342. Retrieved from PLOS CC BY 4.0 (https://creativecommons.org/licenses/by-sa/4.0/legalcode)
Excellent selectivity was observed between primary benzyl alcohols and secondary ones as well as non-benzylic alcohols in the oxidation reactions.
Sepideh Bahrami-Nasab, Alireza Pourali 2014, 'Polymer-supported dichloroiodate as a new polymeric oxidation reagent for novel andselective oxidation of benzylic alcohols under mild aprotic conditions', Current Chemistry Lettershttp://www.growingscience.com/ccl/online/ccl_2013_24.pdf. Retrieved from DOAJ CC BY 4.0 (https://creativecommons.org/licenses/by-sa/4.0/legalcode)
Various benzylic fluorides react with secondary amines or anilines to form benzylic amines in good yields.
Pier Alexandre Champagne, Alexandre Saint-Martin, Mélina Drouin, Jean-François Paquin 2013, 'Triol-promoted activation of C–F bonds: Amination of benzylic fluorides under highlyconcentrated conditions mediated by 1,1,1-tris(hydroxymethyl)propane', Beilstein Journal of Organic Chemistryhttps://doi.org/10.3762/bjoc.9.283. Retrieved from DOAJ CC BY 4.0 (https://creativecommons.org/licenses/by-sa/4.0/legalcode)
Several benzylic alcohols were oxidized with riboflavin tetraacetate as photocatalyst under blue light irradiation of the reaction mixture.
Martin Obst, Burkhard König 2016, 'Solvent-free, visible-light photocatalytic alcohol oxidations applying an organicphotocatalyst', Beilstein Journal of Organic Chemistryhttps://doi.org/10.3762/bjoc.12.229. Retrieved from DOAJ CC BY 4.0 (https://creativecommons.org/licenses/by-sa/4.0/legalcode)