Tuning Benzylic C-H Functionalization of (Thio)xanthenes with Electrochemistry

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2023 Aug 26

PMID 37630392

Authors

Changji Wang

Na Yang

Chao Li

Jian He

Hongji Li

Affiliations

Soon will be listed here.

Abstract

Here, we report a tunable electrochemical benzylic C-H functionalization of (thio)xanthenes with terminal alkynes and nitriles in the absence of any catalyst or external chemical oxidant. The benzylic C-H functionalization can be well controlled by varying the electrochemical conditions, affording the specific coupling products via C-C and C-N bond formation.

References

Liu S, Klussmann M . Acid promoted radical-chain difunctionalization of styrenes with stabilized radicals and (N,O)-nucleophiles. Chem Commun (Camb). 2020; 56(10):1557-1560. DOI: 10.1039/c9cc09369a. View

Das S, Roy S, Bhowmik A, Sarkar W, Mondal I, Mishra A . A radical-radical cross-coupling reaction of xanthene with sulfonyl hydrazides: facile access to xanthen-9-sulfone derivatives. Chem Commun (Camb). 2022; 58(17):2902-2905. DOI: 10.1039/d1cc07143b. View

Khatua H, Das S, Patra S, Das S, Roy S, Chattopadhyay B . Iron-Catalyzed Intermolecular Amination of Benzylic C(sp)-H Bonds. J Am Chem Soc. 2022; 144(48):21858-21866. DOI: 10.1021/jacs.2c10719. View

Pinter A, Sud A, Sureshkumar D, Klussmann M . Autoxidative carbon-carbon bond formation from carbon-hydrogen bonds. Angew Chem Int Ed Engl. 2010; 49(29):5004-7. DOI: 10.1002/anie.201000711. View

Suh S, Nkulu L, Lin S, Krska S, Stahl S . Benzylic C-H isocyanation/amine coupling sequence enabling high-throughput synthesis of pharmaceutically relevant ureas. Chem Sci. 2021; 12(30):10380-10387. PMC: 8336431. DOI: 10.1039/d1sc02049h. View

Muramatsu W, Nakano K . Efficient C(sp³)-H bond functionalization of isochroman by AZADOL catalysis. Org Lett. 2015; 17(6):1549-52. DOI: 10.1021/acs.orglett.5b00434. View

Ji X, Huang T, Wu W, Liang F, Cao S . LDA-Mediated Synthesis of Triarylmethanes by Arylation of Diarylmethanes with Fluoroarenes at Room Temperature. Org Lett. 2015; 17(20):5096-9. DOI: 10.1021/acs.orglett.5b02602. View

Kawamata Y, Hayashi K, Carlson E, Shaji S, Waldmann D, Simmons B . Chemoselective Electrosynthesis Using Rapid Alternating Polarity. J Am Chem Soc. 2021; 143(40):16580-16588. PMC: 8711284. DOI: 10.1021/jacs.1c06572. View

Tang S, Guillot R, Grimaud L, Vitale M, Vincent G . Electrochemical Benzylic C-H Functionalization with Isocyanides. Org Lett. 2022; 24(11):2125-2130. DOI: 10.1021/acs.orglett.2c00364. View

10.

Yang Y, Wu Y, Song R, Li J . Electrochemical dehydrogenative cross-coupling of xanthenes with ketones. Chem Commun (Camb). 2020; 56(55):7585-7588. DOI: 10.1039/d0cc02580a. View

11.

Zhang W, Wang F, McCann S, Wang D, Chen P, Stahl S . Enantioselective cyanation of benzylic C-H bonds via copper-catalyzed radical relay. Science. 2016; 353(6303):1014-1018. PMC: 5488708. DOI: 10.1126/science.aaf7783. View

12.

Maia M, Resende D, Duraes F, Pinto M, Sousa E . Xanthenes in Medicinal Chemistry - Synthetic strategies and biological activities. Eur J Med Chem. 2020; 210:113085. DOI: 10.1016/j.ejmech.2020.113085. View

13.

Fenteany G, Sharma G, Gaur P, Borics A, Weber E, Kiss E . A series of xanthenes inhibiting Rad6 function and Rad6-Rad18 interaction in the PCNA ubiquitination cascade. iScience. 2022; 25(4):104053. PMC: 8958325. DOI: 10.1016/j.isci.2022.104053. View

14.

Guo S, AbuSalim D, Cook S . Aqueous Benzylic C-H Trifluoromethylation for Late-Stage Functionalization. J Am Chem Soc. 2018; 140(39):12378-12382. PMC: 6310231. DOI: 10.1021/jacs.8b08547. View

15.

Yang Y, Song R, Li J . Intermolecular Anodic Oxidative Cross-Dehydrogenative C(sp)-N Bond-Coupling Reactions of Xanthenes with Azoles. Org Lett. 2019; 21(9):3228-3231. DOI: 10.1021/acs.orglett.9b00947. View

16.

Zhang B, Xiang S, Zhang L, Cui Y, Jiao N . Organocatalytic asymmetric intermolecular dehydrogenative α-alkylation of aldehydes using molecular oxygen as oxidant. Org Lett. 2011; 13(19):5212-5. DOI: 10.1021/ol202090a. View

17.

Bhanuchandra M, Yorimitsu H, Osuka A . Synthesis of Spirocyclic Diarylfluorenes by One-Pot Twofold SNAr Reactions of Diaryl Sulfones with Diarylmethanes. Org Lett. 2016; 18(3):384-7. DOI: 10.1021/acs.orglett.5b03384. View

18.

Lewandowska-Andralojc A, Grills D, Zhang J, Bullock R, Miyazawa A, Kawanishi Y . Kinetic and mechanistic studies of carbon-to-metal hydrogen atom transfer involving Os-centered radicals: evidence for tunneling. J Am Chem Soc. 2014; 136(9):3572-8. DOI: 10.1021/ja4123076. View

19.

Dewanji A, Krach P, Rueping M . The Dual Role of Benzophenone in Visible-Light/Nickel Photoredox-Catalyzed C-H Arylations: Hydrogen-Atom Transfer and Energy Transfer. Angew Chem Int Ed Engl. 2019; 58(11):3566-3570. DOI: 10.1002/anie.201901327. View

20.

Das M, Zamani L, Bratcher C, Musacchio P . Azolation of Benzylic C-H Bonds via Photoredox-Catalyzed Carbocation Generation. J Am Chem Soc. 2023; . PMC: 10409882. DOI: 10.1021/jacs.2c12850. View