Chemo- and Diastereoselective Hydrosilylation of Amorphadiene Toward the Synthesis of Artemisinin

Overview

Journal J Org Chem

Publisher American Chemical Society

Specialty Chemistry

Date 2020 Jul 10

PMID 32643937

Citations 1

Authors

Geoffrey Schwertz

Andrea Zanetti

Marllon Nascimento de Oliveira

Mario Andres Gomez Fernandez

Zacharias Amara

Janine Cossy

Affiliations

Soon will be listed here.

Abstract

A formal synthesis of artemisinin starting from amorphadiene is described. This new route relies on the development of a catalytic chemo- and diastereoselective hydrosilylation. The practicability of this method is demonstrated by converting amorphadiene to dihydroartemisinic aldehyde using a one-pot hydrosilylation/oxidation sequence, minimizing the number of purifications and maximizing the productivity through a practical one-pot procedure. In addition, this approach can be coupled with a crystallization-induced diastereoselective transformation (CIDT) to enhance the optical purity of the key target intermediate, dihydroartemisinic aldehyde.

Citing Articles

Site-Selective Functionalization of Unactivated Allylic C-H Bonds via Direct Deprotonation with KTMP: Application to the Formal Total Synthesis of (+)-Artemisinin from Amorphadiene.

Clanton N, Wilson N, Ortiz E, Blumberg S, Frantz D Org Lett. 2023; 25(1):277-281.

PMID: 36592432 PMC: 9841608. DOI: 10.1021/acs.orglett.2c04145.

References

Zanetti A, Chaumont-Olive P, Schwertz G, de Oliveira M, Gomez Fernandez M, Amara Z . Crystallization-Induced Diastereoisomer Transformation of Dihydroartemisinic Aldehyde with the Betti Base. Org Process Res Dev. 2020; 24(5):850-855. PMC: 7237042. DOI: 10.1021/acs.oprd.9b00481. View

Matsumoto K, Shimada S, Sato K . Sequence-Controlled Catalytic One-Pot Synthesis of Siloxane Oligomers. Chemistry. 2018; 25(4):920-928. DOI: 10.1002/chem.201803565. View

Triemer S, Gilmore K, Vu G, Seeberger P, Seidel-Morgenstern A . Literally Green Chemical Synthesis of Artemisinin from Plant Extracts. Angew Chem Int Ed Engl. 2018; 57(19):5525-5528. DOI: 10.1002/anie.201801424. View

Oestreich M, Hermeke J, Mohr J . A unified survey of Si-H and H-H bond activation catalysed by electron-deficient boranes. Chem Soc Rev. 2015; 44(8):2202-20. DOI: 10.1039/c4cs00451e. View

Ni J, Oguro T, Sawazaki T, Sohma Y, Kanai M . Hydroxy Group Directed Catalytic Hydrosilylation of Amides. Org Lett. 2018; 20(23):7371-7374. DOI: 10.1021/acs.orglett.8b03014. View

Saito K, Kondo K, Akiyama T . B(C6F5)3-Catalyzed Hydrodesulfurization Using Hydrosilanes--Metal-Free Reduction of Sulfides. Org Lett. 2015; 17(13):3366-9. DOI: 10.1021/acs.orglett.5b01651. View

Amara Z, Bellamy J, Horvath R, Miller S, Beeby A, Burgard A . Applying green chemistry to the photochemical route to artemisinin. Nat Chem. 2015; 7(6):489-95. DOI: 10.1038/nchem.2261. View

Cao M, Yesilcimen A, Wasa M . Enantioselective Conia-Ene-Type Cyclizations of Alkynyl Ketones through Cooperative Action of B(CF), N-Alkylamine and a Zn-Based Catalyst. J Am Chem Soc. 2019; 141(10):4199-4203. PMC: 6595478. DOI: 10.1021/jacs.8b13757. View

Kung S, Lund S, Murarka A, McPhee D, Paddon C . Approaches and Recent Developments for the Commercial Production of Semi-synthetic Artemisinin. Front Plant Sci. 2018; 9:87. PMC: 5797932. DOI: 10.3389/fpls.2018.00087. View

10.

Hackel T, McGrath N . Tris(pentafluorophenyl)borane-Catalyzed Reactions Using Silanes. Molecules. 2019; 24(3). PMC: 6384582. DOI: 10.3390/molecules24030432. View

11.

Zhang J, Park S, Chang S . Catalytic Access to Bridged Sila- N-heterocycles from Piperidines via Cascade sp and sp C-Si Bond Formation. J Am Chem Soc. 2018; 140(41):13209-13213. DOI: 10.1021/jacs.8b08733. View

12.

Wang G, Gao L, Chen H, Liu X, Cao J, Chen S . Chemoselective Borane-Catalyzed Hydroarylation of 1,3-Dienes with Phenols. Angew Chem Int Ed Engl. 2018; 58(6):1694-1699. DOI: 10.1002/anie.201811729. View

13.

Tu Y . Artemisinin-A Gift from Traditional Chinese Medicine to the World (Nobel Lecture). Angew Chem Int Ed Engl. 2016; 55(35):10210-26. DOI: 10.1002/anie.201601967. View

14.

Lee D, Amara Z, Clark C, Xu Z, Kakimpa B, Morvan H . Continuous Photo-Oxidation in a Vortex Reactor: Efficient Operations Using Air Drawn from the Laboratory. Org Process Res Dev. 2017; 21(7):1042-1050. PMC: 5526652. DOI: 10.1021/acs.oprd.7b00153. View

15.

Welch G, San Juan R, Masuda J, Stephan D . Reversible, metal-free hydrogen activation. Science. 2006; 314(5802):1124-6. DOI: 10.1126/science.1134230. View

16.

Li C, Li J, Wang G, Li X . Heterologous biosynthesis of artemisinic acid in Saccharomyces cerevisiae. J Appl Microbiol. 2016; 120(6):1466-78. DOI: 10.1111/jam.13044. View

17.

Rubin M, Schwier T, Gevorgyan V . Highly efficient B(C(6)F(5))(3)-catalyzed hydrosilylation of olefins. J Org Chem. 2002; 67(6):1936-40. DOI: 10.1021/jo016279z. View

18.

Gevorgyan V, Rubin M, Liu J, Yamamoto Y . A direct reduction of aliphatic aldehyde, acyl chloride, ester, and carboxylic functions into a methyl group. J Org Chem. 2001; 66(5):1672-5. DOI: 10.1021/jo001258a. View

19.

Bezier D, Park S, Brookhart M . Selective reduction of carboxylic acids to aldehydes catalyzed by B(C6F5)3. Org Lett. 2013; 15(3):496-9. DOI: 10.1021/ol303296a. View

20.

Brook M . New Control Over Silicone Synthesis using SiH Chemistry: The Piers-Rubinsztajn Reaction. Chemistry. 2018; 24(34):8458-8469. DOI: 10.1002/chem.201800123. View