Rhodium(iii)-catalyzed Synthesis of Phthalides by Cascade Addition and Cyclization of Benzimidates with Aldehydes

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2012 Oct 11

PMID 23050074

Citations 8

Authors

Yajing Lian

Robert G Bergman

Jonathan A Ellman

Affiliations

Soon will be listed here.

Abstract

We herein report the Rh(iii)-catalyzed C-H bond activation and addition of benzimidates to aldehydes to afford biologically important phthalides in a single step. The imidate is a novel and unexplored directing group that not only enables C-H bond activation and addition to aldehydes, but also serves to capture the reversibly formed alcohol intermediate. The reaction shows broad scope with a high level of functional group compatibility and is applicable to both aromatic and aliphatic aldehydes.

Citing Articles

Synthesis of Phthalides and α,β-butenolides by Transition Metal-Catalyzed Activation of C-H Bonds.

Renzetti A, Fukumoto K Molecules. 2019; 24(4).

PMID: 30823615 PMC: 6412913. DOI: 10.3390/molecules24040824.

Transition-Metal-Catalyzed C-H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds.

Hummel J, Boerth J, Ellman J Chem Rev. 2016; 117(13):9163-9227.

PMID: 27936637 PMC: 5468517. DOI: 10.1021/acs.chemrev.6b00661.

Rh(III)-Catalyzed Diastereoselective C-H Bond Addition/Cyclization Cascade of Enone Tethered Aldehydes.

Boerth J, Ellman J Chem Sci. 2016; 7(2):1474-1479.

PMID: 26918112 PMC: 4762265. DOI: 10.1039/C5SC04138D.

Cobalt(III)-Catalyzed C-H Bond Amidation with Isocyanates.

Hummel J, Ellman J Org Lett. 2015; 17(10):2400-3.

PMID: 25945401 PMC: 4460580. DOI: 10.1021/acs.orglett.5b00910.

Cobalt(III)-catalyzed synthesis of indazoles and furans by C-H bond functionalization/addition/cyclization cascades.

Hummel J, Ellman J J Am Chem Soc. 2014; 137(1):490-8.

PMID: 25494296 PMC: 4304451. DOI: 10.1021/ja5116452.

References

Colby D, Bergman R, Ellman J . Rhodium-catalyzed C-C bond formation via heteroatom-directed C-H bond activation. Chem Rev. 2009; 110(2):624-55. PMC: 2820156. DOI: 10.1021/cr900005n. View

Zhou C, Larock R . Synthesis of aryl ketones by the PD-catalyzed C-H activation of arenes and intermolecular carbopalladation of nitriles. J Am Chem Soc. 2004; 126(8):2302-3. DOI: 10.1021/ja038687l. View

Wrigglesworth J, Cox B, Lloyd-Jones G, Booker-Milburn K . New heteroannulation reactions of N-alkoxybenzamides by Pd(II) catalyzed C-H activation. Org Lett. 2011; 13(19):5326-9. DOI: 10.1021/ol202187h. View

Ng K, Chan A, Yu W . Pd-catalyzed intermolecular ortho-C-H amidation of anilides by N-nosyloxycarbamate. J Am Chem Soc. 2010; 132(37):12862-4. DOI: 10.1021/ja106364r. View

Zhou B, Yang Y, Li Y . Rhodium-catalyzed oxidative C2-acylation of indoles with aryl and alkyl aldehydes. Chem Commun (Camb). 2012; 48(42):5163-5. DOI: 10.1039/c2cc31351k. View

Tsai A, Brasse M, Bergman R, Ellman J . Rh(III)-catalyzed oxidative coupling of unactivated alkenes via C-H activation. Org Lett. 2010; 13(3):540-2. PMC: 3031716. DOI: 10.1021/ol102890k. View

Guimond N, Gorelsky S, Fagnou K . Rhodium(III)-catalyzed heterocycle synthesis using an internal oxidant: improved reactivity and mechanistic studies. J Am Chem Soc. 2011; 133(16):6449-57. DOI: 10.1021/ja201143v. View

Rakshit S, Patureau F, Glorius F . Pyrrole synthesis via allylic sp3 C-H activation of enamines followed by intermolecular coupling with unactivated alkynes. J Am Chem Soc. 2010; 132(28):9585-7. DOI: 10.1021/ja104305s. View

Zhu C, Xie W, Falck J . Rhodium-catalyzed annulation of N-benzoylsulfonamide with isocyanide through C-H activation. Chemistry. 2011; 17(45):12591-5. PMC: 3426457. DOI: 10.1002/chem.201102475. View

10.

Li H, Li Y, Zhang X, Chen K, Wang X, Shi Z . Pyridinyl directed alkenylation with olefins via Rh(III)-catalyzed C-C bond cleavage of secondary arylmethanols. J Am Chem Soc. 2011; 133(39):15244-7. DOI: 10.1021/ja205228y. View

11.

Hesp K, Bergman R, Ellman J . Rhodium-catalyzed synthesis of branched amines by direct addition of benzamides to imines. Org Lett. 2012; 14(9):2304-7. PMC: 3345069. DOI: 10.1021/ol300723x. View

12.

Neufeldt S, Sanford M . O-acetyl oximes as transformable directing groups for Pd-catalyzed C-H bond functionalization. Org Lett. 2010; 12(3):532-5. PMC: 2830615. DOI: 10.1021/ol902720d. View

13.

Xiao F, Shuai Q, Zhao F, Basle O, Deng G, Li C . Palladium-catalyzed oxidative sp2 C-H bond acylation with alcohols. Org Lett. 2011; 13(7):1614-7. DOI: 10.1021/ol200017a. View

14.

Martin R, Bergman R, Ellman J . Synthesis of pyridines from ketoximes and terminal alkynes via C-H bond functionalization. J Org Chem. 2012; 77(5):2501-7. PMC: 3292635. DOI: 10.1021/jo202280e. View

15.

Gerfaud T, Neuville L, Zhu J . Palladium-catalyzed annulation of acyloximes with arynes (or alkynes): synthesis of phenanthridines and isoquinolines. Angew Chem Int Ed Engl. 2008; 48(3):572-7. DOI: 10.1002/anie.200804683. View

16.

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

17.

Ackermann L, Pospech J . Ruthenium-catalyzed oxidative C-H bond alkenylations in water: expedient synthesis of annulated lactones. Org Lett. 2011; 13(16):4153-5. DOI: 10.1021/ol201563r. View

18.

Hyster T, Rovis T . Pyridine synthesis from oximes and alkynes via rhodium(III) catalysis: Cp* and Cp(t) provide complementary selectivity. Chem Commun (Camb). 2011; 47(43):11846-8. PMC: 3430144. DOI: 10.1039/c1cc15248c. View

19.

Beck J, Chou S . The structural diversity of phthalides from the Apiaceae. J Nat Prod. 2007; 70(5):891-900. DOI: 10.1021/np0605586. View

20.

Patureau F, Glorius F . Oxidizing directing groups enable efficient and innovative C-H activation reactions. Angew Chem Int Ed Engl. 2011; 50(9):1977-9. DOI: 10.1002/anie.201007241. View