Reversible Bergman Cyclization by Atomic Manipulation

Overview

Journal Nat Chem

Specialty Chemistry

Date 2016 Feb 20

PMID 26892552

Citations 36

Authors

Bruno Schuler

Shadi Fatayer

Fabian Mohn

Nikolaj Moll

Niko Pavlicek

Gerhard Meyer

Diego Pena

Leo Gross

Affiliations

Soon will be listed here.

Abstract

The Bergman cyclization is one of the most fascinating rearrangements in chemistry, with important implications in organic synthesis and pharmacology. Here we demonstrate a reversible Bergman cyclization for the first time. We induced the on-surface transformation of an individual aromatic diradical into a highly strained ten-membered diyne using atomic manipulation and verified the products by non-contact atomic force microscopy with atomic resolution. The diyne and diradical were stabilized by using an ultrathin NaCl film as the substrate, and the diyne could be transformed back into the diradical. Importantly, the diradical and the diyne exhibit different reactivity, electronic, magnetic and optical properties associated with the changes in the bond topology, and spin multiplicity. With this reversible, triggered Bergman cyclization we demonstrated switching on demand between the two reactive intermediates by means of selective C-C bond formation or cleavage, which opens up the field of radical chemistry for on-surface reactions by atomic manipulation.

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References

Moll N, Schuler B, Kawai S, Xu F, Peng L, Orita A . Image distortions of a partially fluorinated hydrocarbon molecule in atomic force microscopy with carbon monoxide terminated tips. Nano Lett. 2014; 14(11):6127-31. DOI: 10.1021/nl502113z. View

Gross L, Mohn F, Moll N, Meyer G, Ebel R, Abdel-Mageed W . Organic structure determination using atomic-resolution scanning probe microscopy. Nat Chem. 2010; 2(10):821-5. DOI: 10.1038/nchem.765. View

Lafferentz L, Eberhardt V, Dri C, Africh C, Comelli G, Esch F . Controlling on-surface polymerization by hierarchical and substrate-directed growth. Nat Chem. 2012; 4(3):215-20. DOI: 10.1038/nchem.1242. View

Perdew , Burke , Ernzerhof . Generalized Gradient Approximation Made Simple. Phys Rev Lett. 1996; 77(18):3865-3868. DOI: 10.1103/PhysRevLett.77.3865. View

Grill L, Dyer M, Lafferentz L, Persson M, Peters M, Hecht S . Nano-architectures by covalent assembly of molecular building blocks. Nat Nanotechnol. 2008; 2(11):687-91. DOI: 10.1038/nnano.2007.346. View

Nicolaou K, Smith A, Yue E . Chemistry and biology of natural and designed enediynes. Proc Natl Acad Sci U S A. 1993; 90(13):5881-8. PMC: 46830. DOI: 10.1073/pnas.90.13.5881. View

Repp J, Meyer G, Stojkovic S, Gourdon A, Joachim C . Molecules on insulating films: scanning-tunneling microscopy imaging of individual molecular orbitals. Phys Rev Lett. 2005; 94(2):026803. DOI: 10.1103/PhysRevLett.94.026803. View

Tkatchenko A, Scheffler M . Accurate molecular van der Waals interactions from ground-state electron density and free-atom reference data. Phys Rev Lett. 2009; 102(7):073005. DOI: 10.1103/PhysRevLett.102.073005. View

Nicolaou K, Dai W, Tsay S, Estevez V, Wrasidlo W . Designed enediynes: a new class of DNA-cleaving molecules with potent and selective anticancer activity. Science. 1992; 256(5060):1172-8. DOI: 10.1126/science.256.5060.1172. View

10.

Mohn F, Repp J, Gross L, Meyer G, Dyer M, Persson M . Reversible bond formation in a gold-atom-organic-molecule complex as a molecular switch. Phys Rev Lett. 2011; 105(26):266102. DOI: 10.1103/PhysRevLett.105.266102. View

11.

Repp J, Meyer G, Paavilainen S, Olsson F, Persson M . Imaging bond formation between a gold atom and pentacene on an insulating surface. Science. 2006; 312(5777):1196-9. DOI: 10.1126/science.1126073. View

12.

Cai J, Ruffieux P, Jaafar R, Bieri M, Braun T, Blankenburg S . Atomically precise bottom-up fabrication of graphene nanoribbons. Nature. 2010; 466(7305):470-3. DOI: 10.1038/nature09211. View

13.

Pavlicek N, Fleury B, Neu M, Niedenfuhr J, Herranz-Lancho C, Ruben M . Atomic force microscopy reveals bistable configurations of dibenzo[a,h]thianthrene and their interconversion pathway. Phys Rev Lett. 2012; 108(8):086101. DOI: 10.1103/PhysRevLett.108.086101. View

14.

Albrecht F, Neu M, Quest C, Swart I, Repp J . Formation and characterization of a molecule-metal-molecule bridge in real space. J Am Chem Soc. 2013; 135(24):9200-3. DOI: 10.1021/ja404084p. View

15.

Pavlicek N, Schuler B, Collazos S, Moll N, Perez D, Guitian E . On-surface generation and imaging of arynes by atomic force microscopy. Nat Chem. 2015; 7(8):623-8. DOI: 10.1038/nchem.2300. View

16.

Gross L, Mohn F, Moll N, Liljeroth P, Meyer G . The chemical structure of a molecule resolved by atomic force microscopy. Science. 2009; 325(5944):1110-4. DOI: 10.1126/science.1176210. View

17.

Sun Q, Zhang C, Li Z, Kong H, Tan Q, Hu A . On-surface formation of one-dimensional polyphenylene through Bergman cyclization. J Am Chem Soc. 2013; 135(23):8448-51. DOI: 10.1021/ja404039t. View

18.

Zhang G, Tkatchenko A, Paier J, Appel H, Scheffler M . Van der Waals interactions in ionic and semiconductor solids. Phys Rev Lett. 2012; 107(24):245501. DOI: 10.1103/PhysRevLett.107.245501. View

19.

Sinha S, Li L, Miller G, Dutta S, Rader C, Lerner R . Prodrugs of dynemicin analogs for selective chemotherapy mediated by an aldolase catalytic Ab. Proc Natl Acad Sci U S A. 2004; 101(9):3095-9. PMC: 365749. DOI: 10.1073/pnas.0307319101. View

20.

Wenk H, Winkler M, Sander W . One century of aryne chemistry. Angew Chem Int Ed Engl. 2003; 42(5):502-28. DOI: 10.1002/anie.200390151. View