Efficient Synthesis of 3H-indoles Enabled by the Lead-mediated α-arylation of β-ketoesters or γ-lactams Using Aryl Azides

Overview

Journal Org Lett

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2014 May 29

PMID 24865180

Citations 1

Authors

Fei Zhou

Tom G Driver

Affiliations

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Abstract

The development of a lead-mediated α-arylation reaction between aryl azides and β-ketoesters or γ-lactams that facilitates the formation of 3H-indoles is disclosed. Twenty-five examples are included which demonstrate the generality of this reaction to access aryl azides bearing tetrasubstituted o-alkyl substituents. When paired with a Staudinger reduction, this reaction streamlines the synthesis of functionalized 3H-indoles.

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References

Ackermann L, Vicente R, Hofmann N . Air-stable secondary phosphine oxide as preligand for palladium-catalyzed intramolecular alpha-arylations with chloroarenes. Org Lett. 2009; 11(19):4274-6. DOI: 10.1021/ol901597d. View

Ooi T, Goto R, Maruoka K . Fluorotetraphenylbismuth: a new reagent for efficient regioselective alpha-phenylation of carbonyl compounds. J Am Chem Soc. 2003; 125(35):10494-5. DOI: 10.1021/ja030150k. View

Aggarwal V, Olofsson B . Enantioselective alpha-arylation of cyclohexanones with diaryl iodonium salts: application to the synthesis of (-)-epibatidine. Angew Chem Int Ed Engl. 2005; 44(34):5516-9. DOI: 10.1002/anie.200501745. View

Pumphrey A, Dong H, Driver T . Rh(II)2-catalyzed synthesis of α-, β-, or δ-carbolines from aryl azides. Angew Chem Int Ed Engl. 2012; 51(24):5920-3. PMC: 3397914. DOI: 10.1002/anie.201201788. View

Chan W, Zhou Z, Yu W . Palladium-catalyzed oxidative direct C-H/C-H cross coupling of anilides with β-keto esters. Chem Commun (Camb). 2013; 49(74):8214-6. DOI: 10.1039/c3cc44769c. View

Chen Y, Xie X, Ma D . Facile access to polysubstituted indoles via a cascade Cu-catalyzed arylation-condensation process. J Org Chem. 2007; 72(24):9329-34. DOI: 10.1021/jo702059q. View

Stokes B, Richert K, Driver T . Examination of the mechanism of Rh(2)(II)-catalyzed carbazole formation using intramolecular competition experiments. J Org Chem. 2009; 74(17):6442-51. PMC: 2883892. DOI: 10.1021/jo901224k. View

Newhouse T, Baran P, Hoffmann R . The economies of synthesis. Chem Soc Rev. 2009; 38(11):3010-21. PMC: 2880393. DOI: 10.1039/b821200g. View

Schmidt A, Reddy K, Knolker H . Occurrence, biogenesis, and synthesis of biologically active carbazole alkaloids. Chem Rev. 2012; 112(6):3193-328. DOI: 10.1021/cr200447s. View

10.

Guillonneau C, PierreA , Charton Y, Guilbaud N, Kraus-Berthier L, Leonce S . Synthesis of 9-O-substituted derivatives of 9-hydroxy-5, 6-dimethyl-6H-pyrido[4,3-b]carbazole-1-carboxylic acid (2-(dimethylamino)ethyl)amide and their 10- and 11-methyl analogues with improved antitumor activity. J Med Chem. 1999; 42(12):2191-203. DOI: 10.1021/jm981093m. View

11.

Huang Z, Chen Z, Lim L, Quang G, Hirao H, Zhou J . Weak arene C-H···O hydrogen bonding in palladium-catalyzed arylation and vinylation of lactones. Angew Chem Int Ed Engl. 2013; 52(22):5807-12. DOI: 10.1002/anie.201300481. View

12.

Wu L, Falivene L, Drinkel E, Grant S, Linden A, Cavallo L . Synthesis of 3-fluoro-3-aryl oxindoles: direct enantioselective α arylation of amides. Angew Chem Int Ed Engl. 2012; 51(12):2870-3. DOI: 10.1002/anie.201200206. View

13.

Sun K, Sachwani R, Richert K, Driver T . Intramolecular Ir(I)-catalyzed benzylic C-H bond amination of ortho-substituted aryl azides. Org Lett. 2009; 11(16):3598-601. PMC: 2743533. DOI: 10.1021/ol901317j. View

14.

Mohanan K, Coquerel Y, Rodriguez J . Transition-metal-free α-arylation of β-keto amides via an interrupted insertion reaction of arynes. Org Lett. 2012; 14(17):4686-9. DOI: 10.1021/ol302180v. View

15.

Wender P, Verma V, Paxton T, Pillow T . Function-oriented synthesis, step economy, and drug design. Acc Chem Res. 2007; 41(1):40-9. DOI: 10.1021/ar700155p. View

16.

Zheng B, Jia T, Walsh P . Palladium-catalyzed direct intermolecular α-arylation of amides with aryl chlorides. Org Lett. 2013; 15(16):4190-3. DOI: 10.1021/ol4019002. View

17.

Stokes B, Dong H, Leslie B, Pumphrey A, Driver T . Intramolecular C-H amination reactions: exploitation of the Rh(2)(II)-catalyzed decomposition of azidoacrylates. J Am Chem Soc. 2007; 129(24):7500-1. DOI: 10.1021/ja072219k. View

18.

Wang H, Anderson L . Interrupted Fischer-indole intermediates via oxyarylation of alkenyl boronic acids. Org Lett. 2013; 15(13):3362-5. DOI: 10.1021/ol401416r. View

19.

Knolker H, Reddy K . Chemistry and biology of carbazole alkaloids. Alkaloids Chem Biol. 2008; 65:1-410. DOI: 10.1016/s1099-4831(07)00001-6. View

20.

Xie X, Chen Y, Ma D . Enantioselective arylation of 2-methylacetoacetates catalyzed by CuI/trans-4-hydroxy-L-proline at low reaction temperatures. J Am Chem Soc. 2006; 128(50):16050-1. DOI: 10.1021/ja066991j. View