[2+2+2] Annulation of -(1-Naphthyl)acetamide with Two Alkynoates Via Cleavage of Adjacent C⁻H and C⁻N Bonds Catalyzed by an Electron-Deficient Rhodium(III) Complex

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2018 Dec 19

PMID 30558193

Authors

Jyunichi Terasawa

Yu Shibata

Miho Fukui

Ken Tanaka

Affiliations

Soon will be listed here.

Abstract

It has been established that an electron-deficient cationic Cp-rhodium(III) complex catalyzes the non-oxidative [2+2+2] annulation of -(1-naphthyl)acetamide with two alkynoates via cleavage of the adjacent C⁻H and C⁻N bonds to give densely substituted phenanthrenes under mild conditions (at 40 °C under air). In this reaction, a dearomatized spiro compound was isolated, which may support the formation of a cationic spiro rhodacycle intermediate in the catalytic cycle. The use of -(1-naphthyl)acetamide in place of acetanilide switched the reaction pathway from the oxidative [2+2+2] annulation-lactamization via C⁻H/C⁻H cleavage to the non-oxidative [2+2+2] annulation via C⁻H/C⁻N cleavage. This chemoselectivity switch may arise from stabilization of the carbocation in the above cationic spiro rhodacycle by the neighboring phenyl and acetylamino groups, resulting in the nucleophilic C⁻C bond formation followed by β-nitrogen elimination.

References

Dieter R, Lu K . Alpha-(N-carbamoyl)alkylcuprate chemistry in the synthesis of nitrogen heterocycles. J Org Chem. 2002; 67(3):847-55. DOI: 10.1021/jo016053w. View

Maezaki N, Yagi S, Yoshigami R, Maeda J, Suzuki T, Ohsawa S . Pd-catalyzed sulfinylzincation of activated alkynes with 1-alkynyl sulfoxides as a sulfinyl source. J Org Chem. 2003; 68(14):5550-8. DOI: 10.1021/jo034108j. View

Hsieh J, Cheng C . Nickel-catalyzed cocyclotrimerization of arynes with diynes; a novel method for synthesis of naphthalene derivatives. Chem Commun (Camb). 2005; (19):2459-61. DOI: 10.1039/b415691a. View

Ueura K, Satoh T, Miura M . Rhodium- and iridium-catalyzed oxidative coupling of benzoic acids with alkynes via regioselective C-H bond cleavage. J Org Chem. 2007; 72(14):5362-7. DOI: 10.1021/jo070735n. View

Hsieh J, Cheng C . o-Dihaloarenes as aryne precursors for nickel-catalyzed [2 + 2 + 2] cycloaddition with alkynes and nitriles. Chem Commun (Camb). 2008; (26):2992-4. DOI: 10.1039/b801870g. View

Galan B, Rovis T . Beyond Reppe: building substituted arenes by [2+2+2] cycloadditions of alkynes. Angew Chem Int Ed Engl. 2009; 48(16):2830-4. PMC: 2898745. DOI: 10.1002/anie.200804651. View

Dominguez G, Perez-Castells J . Recent advances in [2+2+2] cycloaddition reactions. Chem Soc Rev. 2011; 40(7):3430-44. DOI: 10.1039/c1cs15029d. View

Weding N, Hapke M . Preparation and synthetic applications of alkene complexes of group 9 transition metals in [2+2+2] cycloaddition reactions. Chem Soc Rev. 2011; 40(9):4525-38. DOI: 10.1039/c0cs00189a. View

Song G, Gong X, Li X . Synthesis of quinolines via Rh(III)-catalyzed oxidative annulation of pyridines. J Org Chem. 2011; 76(18):7583-9. DOI: 10.1021/jo201266u. View

10.

Li X, Gong X, Zhao M, Song G, Deng J, Li X . Rh(III)-catalyzed oxidative olefination of N-(1-naphthyl)sulfonamides using activated and unactivated alkenes. Org Lett. 2011; 13(21):5808-11. DOI: 10.1021/ol2023856. View

11.

Qi Z, Li X . Rhodium(III)-catalyzed coupling of arenes with 7-oxa/azabenzonorbornadienes by C-H activation. Angew Chem Int Ed Engl. 2013; 52(34):8995-9000. DOI: 10.1002/anie.201303507. View

12.

Pham M, Cramer N . Aromatic homologation by non-chelate-assisted Rh(III)-catalyzed C-H functionalization of arenes with alkynes. Angew Chem Int Ed Engl. 2014; 53(13):3484-7. DOI: 10.1002/anie.201310723. View

13.

Dominguez G, Perez-Castells J . Alkenes in [2+2+2] Cycloadditions. Chemistry. 2016; 22(20):6720-39. DOI: 10.1002/chem.201504987. View

14.

Fukui M, Shibata Y, Hoshino Y, Sugiyama H, Teraoka K, Uekusa H . Rhodium(III)-Catalyzed Tandem [2+2+2] Annulation-Lactamization of Anilides with Two Alkynoates via Cleavage of Two Adjacent C-H or C-H/C-O bonds. Chem Asian J. 2016; 11(16):2260-4. DOI: 10.1002/asia.201600943. View

15.

Zhang X, Yu X, Feng X, Yamamoto Y, Almansour A, Arumugam N . Rhodium-Catalyzed Oxidative Benzannulation of N-Pivaloylanilines with Internal Alkynes through Dual C-H Bond Activation: Synthesis of Highly Substituted Naphthalenes. Chem Asian J. 2016; 11(22):3241-3250. DOI: 10.1002/asia.201601131. View

16.

Honjo Y, Shibata Y, Kudo E, Namba T, Masutomi K, Tanaka K . Room Temperature Decarboxylative and Oxidative [2+2+2] Annulation of Benzoic Acids with Alkynes Catalyzed by an Electron-Deficient Rhodium(III) Complex. Chemistry. 2017; 24(2):317-321. DOI: 10.1002/chem.201703928. View