Regioselective Addition/annulation of Ferrocenyl Thioamides with 1,3-diynes a Sulfur-transfer Rearrangement to Construct Extended π-conjugated Ferrocenes with Luminescent Properties

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2021 Jun 14

PMID 34123193

Citations 1

Authors

Lipeng Yan

Jingbo Lan

Hu Cheng

Yihang Li

Mangang Zhang

Di Wu

Jingsong You

Affiliations

Soon will be listed here.

Abstract

Herein a regioselective addition/annulation strategy of ferrocenyl (Fc) thioamides with alkynes to construct thienylferrocene (ThienylFc) structures, involving a rhodium-catalyzed C-H activation, an unusual C2-selective addition of 1,3-diyne, and an unexpected intramolecular sulfur-transfer rearrangement process is described. In this protocol, thioamide not only serves as a directing group to activate the -C-H bond of the ferrocene, but also as a sulfur source to form the thiophene ring. The resulting carboxylic ester group after sulfur transfer can act as a linkage to construct extended π-conjugated ferrocenes (OCTFc) with luminescent properties. ThienylFc displays effective fluorescence quenching due to the photoinduced electron transfer (PET) from the Fc unit to the excited luminophore, which turns out to be a promising type of redox molecular switch. OCTFc exhibit relatively strong emission owing to their intramolecular charge transfer (ICT) characteristics. The ring-fused strategy is herein employed for the first time to construct luminescent materials based on ferrocenes, which provides inspiration for the development of novel organic optoelectronic materials, such as electroluminescent materials based on ferrocenes.

Citing Articles

Harnessing sulfur and nitrogen in the cobalt(iii)-catalyzed unsymmetrical double annulation of thioamides: probing the origin of chemo- and regio-selectivity.

Shankar M, Saha A, Sau S, Ghosh A, Gandon V, Sahoo A Chem Sci. 2021; 12(18):6393-6405.

PMID: 34084439 PMC: 8115082. DOI: 10.1039/d1sc00765c.

References

Jiang H, Zeng W, Li Y, Wu W, Huang L, Fu W . Copper(I)-catalyzed synthesis of 2,5-disubstituted furans and thiophenes from haloalkynes or 1,3-diynes. J Org Chem. 2012; 77(11):5179-83. DOI: 10.1021/jo300692d. View

Shibata T, Shizuno T . Iridium-catalyzed enantioselective C-H alkylation of ferrocenes with alkenes using chiral diene ligands. Angew Chem Int Ed Engl. 2014; 53(21):5410-3. DOI: 10.1002/anie.201402518. View

Chen T, Wang D, Gan L, Matsuo Y, Gu J, Yan H . Direct probing of the structure and electron transfer of fullerene/ferrocene hybrid on Au(111) electrodes by in situ electrochemical STM. J Am Chem Soc. 2014; 136(8):3184-91. DOI: 10.1021/ja411813r. View

Cai Z, Liu C, Wang Q, Gu Q, You S . Thioketone-directed rhodium(I) catalyzed enantioselective C-H bond arylation of ferrocenes. Nat Commun. 2019; 10(1):4168. PMC: 6744407. DOI: 10.1038/s41467-019-12181-x. View

Gao D, Gu Q, You S . An Enantioselective Oxidative C-H/C-H Cross-Coupling Reaction: Highly Efficient Method To Prepare Planar Chiral Ferrocenes. J Am Chem Soc. 2016; 138(8):2544-7. DOI: 10.1021/jacs.6b00127. View

Yetra S, Rogge T, Warratz S, Struwe J, Peng W, Vana P . Micellar Catalysis for Ruthenium(II)-Catalyzed C-H Arylation: Weak-Coordination-Enabled C-H Activation in H O. Angew Chem Int Ed Engl. 2019; 58(22):7490-7494. DOI: 10.1002/anie.201901856. View

Pammer F, Sun Y, Pagels M, Weismann D, Sitzmann H, Thiel W . Dibenzo[c,g]fluorenyliron: an organometallic relative of pentahelicene. Angew Chem Int Ed Engl. 2008; 47(17):3271-4. DOI: 10.1002/anie.200705743. View

Pietschnig R . Polymers with pendant ferrocenes. Chem Soc Rev. 2016; 45(19):5216-31. DOI: 10.1039/c6cs00196c. View

Martinez R, Ratera I, Tarraga A, Molina P, Veciana J . A simple and robust reversible redox-fluorescence molecular switch based on a 1,4-disubstituted azine with ferrocene and pyrene units. Chem Commun (Camb). 2006; (36):3809-11. DOI: 10.1039/b608264e. View

10.

Yu D, de Azambuja F, Gensch T, Daniliuc C, Glorius F . The C-H activation/1,3-diyne strategy: highly selective direct synthesis of diverse bisheterocycles by Rh(III) catalysis. Angew Chem Int Ed Engl. 2014; 53(36):9650-4. DOI: 10.1002/anie.201403782. View

11.

Yin J, Tan M, Wu D, Jiang R, Li C, You J . Synthesis of Phenalenyl-Fused Pyrylium Cations: Divergent C-H Activation/Annulation Reaction Sequence of Naphthalene Aldehydes with Alkynes. Angew Chem Int Ed Engl. 2017; 56(42):13094-13098. DOI: 10.1002/anie.201708127. View

12.

Genet C, Canipa S, OBrien P, Taylor S . Catalytic asymmetric synthesis of ferrocenes and P-stereogenic bisphosphines. J Am Chem Soc. 2006; 128(29):9336-7. DOI: 10.1021/ja062616f. View

13.

Schipper D, Moh L, Muller P, Swager T . Dithiolodithiole as a building block for conjugated materials. Angew Chem Int Ed Engl. 2014; 53(23):5847-51. DOI: 10.1002/anie.201310290. View

14.

Spangler J, Kobayashi Y, Verma P, Wang D, Yu J . α-Arylation of Saturated Azacycles and N-Methylamines via Palladium(II)-Catalyzed C(sp(3))-H Coupling. J Am Chem Soc. 2015; 137(37):11876-9. PMC: 4822695. DOI: 10.1021/jacs.5b06740. View

15.

Drolen C, Conklin E, Hetterich S, Krishnamurthy A, Andrade G, DiMeglio J . pH-Driven Mechanistic Switching from Electron Transfer to Energy Transfer between [Ru(bpy)] and Ferrocene Derivatives. J Am Chem Soc. 2018; 140(32):10169-10178. PMC: 6192533. DOI: 10.1021/jacs.8b03933. View

16.

Cho S, Kim J, Kwak J, Chang S . Recent advances in the transition metal-catalyzed twofold oxidative C-H bond activation strategy for C-C and C-N bond formation. Chem Soc Rev. 2011; 40(10):5068-83. DOI: 10.1039/c1cs15082k. View

17.

Liu Y, Li P, Yao Q, Zhang Z, Huang D, Le M . Cp*Co(III)/MPAA-Catalyzed Enantioselective Amidation of Ferrocenes Directed by Thioamides under Mild Conditions. Org Lett. 2019; 21(6):1895-1899. DOI: 10.1021/acs.orglett.9b00511. View

18.

Cai Z, Liu C, Gu Q, You S . Thioketone-Directed Palladium(II)-Catalyzed C-H Arylation of Ferrocenes with Aryl Boronic Acids. Angew Chem Int Ed Engl. 2017; 57(5):1296-1299. DOI: 10.1002/anie.201711451. View

19.

Lavallo V, Frey G, Donnadieu B, Soleilhavoup M, Bertrand G . Homogeneous catalytic hydroamination of alkynes and allenes with ammonia. Angew Chem Int Ed Engl. 2008; 47(28):5224-8. PMC: 2529152. DOI: 10.1002/anie.200801136. View

20.

Hu B, Meng M, Wang Z, Du W, Fossey J, Hu X . A highly selective ferrocene-based planar chiral PIP (Fc-PIP) acyl transfer catalyst for the kinetic resolution of alcohols. J Am Chem Soc. 2010; 132(47):17041-4. DOI: 10.1021/ja108238a. View