Modular Enantioselective Synthesis of -Cyclopropanes Through Self-Sensitized Stereoselective Photodecarboxylation with Benzothiazolines

Overview

Journal ACS Catal

Publisher American Chemical Society

Date 2021 Nov 12

PMID 34765283

Citations 7

Authors

Matteo Costantini

Abraham Mendoza

Affiliations

Soon will be listed here.

Abstract

Chiral -cyclopropanes are strained rigid analogues of alkyl chains, whose study and application are limited by their difficult synthesis. A modular approach from olefin materials is enabled by the discovery of the electron donor-acceptor (EDA) interaction between 2-substituted benzothiazolines and -hydroxyphthalimide esters. These complexes are activated by visible light without photocatalysts, and the benzothiazoline reagent plays a triple role as a photoreductant, a stereoselective hydrogen-atom donor, and a Brønsted acid. Beyond the enantioselective synthesis of -cyclopropanes, these results introduce benzothiazolines as accessible and easily tunable self-sensitized photoreductants.

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References

Doyle M, Forbes D . Recent Advances in Asymmetric Catalytic Metal Carbene Transformations. Chem Rev. 2002; 98(2):911-936. DOI: 10.1021/cr940066a. View

Knight A, Kan S, Lewis R, Brandenberg O, Chen K, Arnold F . Diverse Engineered Heme Proteins Enable Stereodivergent Cyclopropanation of Unactivated Alkenes. ACS Cent Sci. 2018; 4(3):372-377. PMC: 5879470. DOI: 10.1021/acscentsci.7b00548. View

Carden R, Widenhoefer R . Gold Sulfonium Benzylide Complexes Undergo Efficient Benzylidene Transfer to Alkenes. Chemistry. 2019; 25(47):11026-11030. DOI: 10.1002/chem.201902845. View

Solorio-Alvarado C, Wang Y, Echavarren A . Cyclopropanation with gold(I) carbenes by retro-Buchner reaction from cycloheptatrienes. J Am Chem Soc. 2011; 133(31):11952-5. DOI: 10.1021/ja205046h. View

Wang P, Chen J, Xiao W . Hantzsch esters: an emerging versatile class of reagents in photoredox catalyzed organic synthesis. Org Biomol Chem. 2019; 17(29):6936-6951. DOI: 10.1039/c9ob01289c. View

Chowdhury R, Yu Z, Tong M, Kohlhepp S, Yin X, Mendoza A . Decarboxylative Alkyl Coupling Promoted by NADH and Blue Light. J Am Chem Soc. 2020; 142(47):20143-20151. PMC: 7705967. DOI: 10.1021/jacs.0c09678. View

Rosokha S, Kochi J . Fresh look at electron-transfer mechanisms via the donor/acceptor bindings in the critical encounter complex. Acc Chem Res. 2008; 41(5):641-53. DOI: 10.1021/ar700256a. View

Chen D, Pouwer R, Richard J . Recent advances in the total synthesis of cyclopropane-containing natural products. Chem Soc Rev. 2012; 41(13):4631-42. DOI: 10.1039/c2cs35067j. View

Hu W, Timmons D, Doyle M . In search of high stereocontrol for the construction of cis-disubstituted cyclopropane compounds. Total synthesis of a cyclopropane-configured urea-PETT analogue that is a HIV-1 reverse transcriptase inhibitor. Org Lett. 2002; 4(6):901-4. DOI: 10.1021/ol017276b. View

10.

Solorio-Alvarado C, Echavarren A . Gold-catalyzed annulation/fragmentation: formation of free gold carbenes by retro-cyclopropanation. J Am Chem Soc. 2010; 132(34):11881-3. DOI: 10.1021/ja104743k. View

11.

Henseler A, Kato M, Mori K, Akiyama T . Chiral phosphoric acid catalyzed transfer hydrogenation: facile synthetic access to highly optically active trifluoromethylated amines. Angew Chem Int Ed Engl. 2011; 50(35):8180-3. DOI: 10.1002/anie.201103240. View

12.

Qin T, Malins L, Edwards J, Merchant R, Novak A, Zhong J . Nickel-Catalyzed Barton Decarboxylation and Giese Reactions: A Practical Take on Classic Transforms. Angew Chem Int Ed Engl. 2016; 56(1):260-265. PMC: 5295468. DOI: 10.1002/anie.201609662. View

13.

Talele T . The "Cyclopropyl Fragment" is a Versatile Player that Frequently Appears in Preclinical/Clinical Drug Molecules. J Med Chem. 2016; 59(19):8712-8756. DOI: 10.1021/acs.jmedchem.6b00472. View

14.

Suematsu H, Kanchiku S, Uchida T, Katsuki T . Construction of aryliridium-salen complexes: enantio- and cis-selective cyclopropanation of conjugated and nonconjugated olefins. J Am Chem Soc. 2008; 130(31):10327-37. DOI: 10.1021/ja802561t. View

15.

Levesque E, Goudreau S, Charette A . Improved zinc-catalyzed Simmons-Smith reaction: access to various 1,2,3-trisubstituted cyclopropanes. Org Lett. 2014; 16(5):1490-3. DOI: 10.1021/ol500267w. View

16.

Kammer L, Badir S, Hu R, Molander G . Photoactive electron donor-acceptor complex platform for Ni-mediated C(sp)-C(sp) bond formation. Chem Sci. 2021; 12(15):5450-5457. PMC: 8179655. DOI: 10.1039/d1sc00943e. View

17.

Tarantino K, Liu P, Knowles R . Catalytic ketyl-olefin cyclizations enabled by proton-coupled electron transfer. J Am Chem Soc. 2013; 135(27):10022-5. DOI: 10.1021/ja404342j. View

18.

Piou T, Romanov-Michailidis F, Ashley M, Romanova-Michaelides M, Rovis T . Stereodivergent Rhodium(III)-Catalyzed cis-Cyclopropanation Enabled by Multivariate Optimization. J Am Chem Soc. 2018; 140(30):9587-9593. PMC: 6112604. DOI: 10.1021/jacs.8b04243. View

19.

Zhu S, Perman J, Zhang X . Acceptor/acceptor-substituted diazo reagents for carbene transfers: cobalt-catalyzed asymmetric Z-cyclopropanation of alkenes with alpha-nitrodiazoacetates. Angew Chem Int Ed Engl. 2008; 47(44):8460-3. DOI: 10.1002/anie.200803857. View

20.

Rosenberg M, Vlasana K, Sen Gupta N, Wragg D, Tilset M . Highly cis-selective Rh(I)-catalyzed cyclopropanation reactions. J Org Chem. 2011; 76(8):2465-70. DOI: 10.1021/jo102140z. View