Highly Convergent Total Synthesis of (+)-lithospermic Acid Via a Late-stage Intermolecular C-H Olefination

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2011 Mar 30

PMID 21443224

Citations 29

Authors

Dong-Hui Wang

Jin-Quan Yu

Affiliations

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Abstract

The total synthesis of (+)-lithospermic acid is reported, which exploits two successive C-H activation reactions as key steps. Rh-catalyzed carbene C-H insertion reaction utilizing Davies's catalyst was used to forge dihydrobenzofuran core, and a late-stage intermolecular C-H olefination coupled the olefin unit with the dihydrobenzofuran core to construct the molecule in a highly convergent manner.

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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

Engle K, Wang D, Yu J . Constructing multiply substituted arenes using sequential palladium(II)-catalyzed C-H olefination. Angew Chem Int Ed Engl. 2010; 49(35):6169-73. PMC: 3269767. DOI: 10.1002/anie.201002077. View

Bowie Jr A, Trauner D . Total synthesis of (+/-)-rhazinal using novel palladium-catalyzed cyclizations. J Org Chem. 2009; 74(4):1581-6. DOI: 10.1021/jo801791j. View

Cheng T . Cardiovascular effects of Danshen. Int J Cardiol. 2007; 121(1):9-22. DOI: 10.1016/j.ijcard.2007.01.004. View

Jiang R, Lau K, Hon P, Mak T, Woo K, Fung K . Chemistry and biological activities of caffeic acid derivatives from Salvia miltiorrhiza. Curr Med Chem. 2005; 12(2):237-46. DOI: 10.2174/0929867053363397. View

Wang D, Engle K, Shi B, Yu J . Ligand-enabled reactivity and selectivity in a synthetically versatile aryl C-H olefination. Science. 2009; 327(5963):315-9. PMC: 2879878. DOI: 10.1126/science.1182512. View

Lu Y, Foo L . Polyphenolics of Salvia--a review. Phytochemistry. 2002; 59(2):117-40. DOI: 10.1016/s0031-9422(01)00415-0. View

OMalley S, Tan K, Watzke A, Bergman R, Ellman J . Total synthesis of (+)-lithospermic acid by asymmetric intramolecular alkylation via catalytic C-H bond activation. J Am Chem Soc. 2005; 127(39):13496-7. DOI: 10.1021/ja052680h. View

Garg N, Caspi D, Stoltz B . The total synthesis of (+)-dragmacidin F. J Am Chem Soc. 2004; 126(31):9552-3. DOI: 10.1021/ja046695b. View

10.

Watzke A, OMalley S, Bergman R, Ellman J . Reassignment of the configuration of salvianolic acid B and establishment of its identity with lithospermic acid B. J Nat Prod. 2006; 69(8):1231-3. DOI: 10.1021/np060136w. View

11.

Engle K, Wang D, Yu J . Ligand-accelerated C-H activation reactions: evidence for a switch of mechanism. J Am Chem Soc. 2010; 132(40):14137-51. PMC: 2952432. DOI: 10.1021/ja105044s. View

12.

Shigematsu T, Tajima S, Nishikawa T, Murad S, Pinnell S, Nishioka I . Inhibition of collagen hydroxylation by lithospermic acid magnesium salt, a novel compound isolated from Salviae miltiorrhizae Radix. Biochim Biophys Acta. 1994; 1200(1):79-83. DOI: 10.1016/0304-4165(94)90030-2. View

13.

Baran P, Corey E . A short synthetic route to (+)-austamide, (+)-deoxyisoaustamide, and (+)-hydratoaustamide from a common precursor by a novel palladium-mediated indole --> dihydroindoloazocine cyclization. J Am Chem Soc. 2002; 124(27):7904-5. DOI: 10.1021/ja026663t. View

14.

Abd-Elazem I, Chen H, Bates R, Huang R . Isolation of two highly potent and non-toxic inhibitors of human immunodeficiency virus type 1 (HIV-1) integrase from Salvia miltiorrhiza. Antiviral Res. 2002; 55(1):91-106. DOI: 10.1016/s0166-3542(02)00011-6. View

15.

Kurosawa W, Kan T, Fukuyama T . Stereocontrolled total synthesis of (-)-ephedradine A (orantine). J Am Chem Soc. 2003; 125(27):8112-3. DOI: 10.1021/ja036011k. View

16.

Snyder S, Kontes F . Explorations into neolignan biosynthesis: concise total syntheses of helicterin B, helisorin, and helisterculin A from a common intermediate. J Am Chem Soc. 2009; 131(5):1745-52. DOI: 10.1021/ja806865u. View

17.

Beck E, Hatley R, Gaunt M . Synthesis of rhazinicine by a metal-catalyzed C-H bond functionalization strategy. Angew Chem Int Ed Engl. 2008; 47(16):3004-7. DOI: 10.1002/anie.200705005. View

18.

Nicolaou K, Estrada A, Zak M, Lee S, Safina B . A mild and selective method for the hydrolysis of esters with trimethyltin hydroxide. Angew Chem Int Ed Engl. 2005; 44(9):1378-82. DOI: 10.1002/anie.200462207. View

19.

Zhou L, Zuo Z, Sum Chow M . Danshen: an overview of its chemistry, pharmacology, pharmacokinetics, and clinical use. J Clin Pharmacol. 2005; 45(12):1345-59. DOI: 10.1177/0091270005282630. View