Autocatalysis in Eschenmoser Coupling Reactions
Status PubMed-not-MEDLINE Language English Country Germany Media print-electronic
Document type Journal Article
Grant support
VI.C.192.044
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
OCENW.KLEIN.348
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
- Keywords
- Autocatalysis, Density functional theory calculations, Flow chemistry, Ion mobility, Mass spectrometry, Reaction mechanisms, Vibrational spectroscopy,
- Publication type
- Journal Article MeSH
The Eschenmoser coupling reaction (ECR) of thioamides with electrophiles is believed to proceed via thiirane intermediates. However, little is known about converting the intermediates into ECR products. Previous mechanistic studies involved external thiophiles to remove the sulfur atom from the intermediates. In this work, an ECR proceeding without any thiophilic agent or base is studied by electrospray ionization-mass spectrometry. ESI-MS enables the detection of the so-far elusive polysulfide species Sn , with n ranging from 2 to 16 sulfur atoms, proposed to be the key species leading to product formation. Integrating observations from ion mobility spectrometry, ion spectroscopy, and reaction monitoring via flow chemistry coupled with mass spectrometry provides a comprehensive understanding of the reaction mechanism and uncovers the autocatalytic nature of the ECR reaction.
See more in PubMed
A. Fischli, A. Eschenmoser, Angew. Chem. Int. Ed. 1967, 6, 866-868.
K. Shiosaki, in Comprehensive Organic Synthesis, (Eds. B. Trost and I. Fleming), Elsevier, 1991, pp. 865-892.
S. Braverman, M. Cherkinsky, in Comprehensive Organic Synthesis II, (Ed. P. Knochel), Elsevier, 2014, pp. 887-943.
S. R. Hussaini, R. R. Chamala, Z. Wang, Tetrahedron. 2015, 71, 6017-6086.
R. E. Ireland, F. R. Brown, J. Org. Chem. 1980, 45, 1868-1880.
B. A. D. Neto, A. A. M. Lapis, A. B. Bernd, D. Russowsky, Tetrahedron 2009, 65, 2484-2496.
E. B. Knott, J. Chem. Soc. 1955, 916-927.
B. Roth, R. Laube, M. Y. Tidwell, B. S. Rauckman, J. Org. Chem. 1980, 45, 3651-3657.
N. D. Koduri, B. Hileman, J. D. Cox, H. Scott, P. Hoang, A. Robbins, K. Bowers, L. Tsebaot, K. Miao, M. Castaneda, M. Coffin, G. Wei, T. D. W. Claridge, K. P. Roberts, S. R. Hussaini, RSC Adv. 2013, 3, 181-188.
R. E. Davis, J. Org. Chem. 1958, 23, 1767-1768.
N. P. Neureiter, F. G. Bordwell, J. Am. Chem. Soc. 1959, 81, 578-580.
D. B. Denney, M. J. Boskin, J. Am. Chem. Soc. 1960, 82, 4736-4738.
R. Kammel, D. Tarabová, B. Brož, V. Hladíková, J. Hanusek, Tetrahedron. 2017, 73, 1861-1866.
L. Marek, L. Kolman, J. Vana, J. Svoboda, J. Hanusek, Beil. J. Org. Chem. 2021, 17, 527-539.
K. P. C. Vollhart, R. G. Bergman, J. Am. Chem. Soc. 1973, 95, 7538-7539.
E. Lutz, J.-F. Biellmann, Tetrahedron Lett. 1985, 26, 2789-2792.
W. Chew, D. N. Harpp, Tetrahedron Lett. 1992, 33, 45-48.
W. Chew, R. C. Hynes, D. N. Harpp, J. Org. Chem. 1993, 58, 4398-4404.
Y. Steudel, R. Steudel, M. W. Wong, Chem. Eur. J. 2002, 8, 217-228.
E. M. Lown, H. S. Sandhu, H. E. Gunning, O. P. Strausz, J. Am. Chem. Soc. 1968, 90, 7164-7165.
W. Chew, D. N. Harpp, J. Org. Chem. 1993, 58, 4405-4410.
R. Huisgen, Phosphorus, Sulfur, and Silicon and the Related Elements. 1989, 43, 63-94.
A. Revesz, D. Schroder, T. A. Rokob, M. Havlik, B. Dolensky, Angew. Chem. Int. Ed. 2011, 50, 2401-2404.
L. P. E. Yunker, Z. Ahmadi, J. R. Logan, W. Wu, T. Li, A. Martindale, A. G. Oliver, J. S. McIndoe, Organometallics. 2018, 37, 4297-4308.
C. M. Choi, A. Kulesza, S. Daly, L. MacAleese, R. Antoine, P. Dugourd, F. Chirot, Rapid Commun. Mass Spectrom. 2019, 33, 28-34.
R. G. Belli, Y. Wu, H. Ji, A. Joshi, L. P. E. Yunker, J. S. McIndoe, L. Rosenberg, Inorg. Chem. 2019, 58, 747-755.
L. Polewski, A. Springer, K. Pagel, C. A. Schalley, Acc. Chem. Res. 2021, 54, 2445-2456.
W. Jiang, A. Schäfer, P. C. Mohr, C. A. Schalley, J. Am. Chem. Soc. 2010, 132, 2309-2320.
K. L. Vikse, J. S. McIndoe, Pure Appl. Chem. 2015, 87, 361-377.
D. Van Craen, W. H. Rath, M. Huth, L. Kemp, C. Rauber, J. M. Wollschlager, C. A. Schalley, A. Valkonen, K. Rissanen, M. Albrecht, J. Am. Chem. Soc. 2017, 139, 16959-16966.
J. Mehara, J. Roithová, Chem. Sci. 2020, 11, 11960-11972.
M. M. Gaye, G. Nagy, D. E. Clemmer, N. L. Pohl, Anal. Chem. 2016, 88, 2335-2344.
S. Poyer, C. Lopin-Bon, J. C. Jacquinet, J. Y. Salpin, R. Daniel, Rapid. Commun. Mass Spectrom. 2017, 31, 2003-2010.
A. Galanti, J. Santoro, R. Mannancherry, Q. Duez, V. Diez-Cabanes, M. Valasek, J. De Winter, J. Cornil, P. Gerbaux, M. Mayor, P. Samori, J. Am. Chem. Soc. 2019, 141, 9273-9283.
J. Jašík, J. Žabka, J. Roithová, D. Gerlich, Int. J. Mass spectrom. 2013, 354-355, 204-210.
J. Roithová, A. Gray, E. Andris, J. Jašík, D. Gerlich, Acc. Chem. Res. 2016, 49, 223-230.
L. Jasíková, M. Anania, S. Hybelbauerová, J. Roithová, J. Am. Chem. Soc. 2015, 137, 13647-13657.
Q. Duez, P. Tinnemans, J. A. A. W. Elemans, J. Roithová, Chem. Sci. 2023, 14, 9759-9769.
G. L. Tripodi, M. T. G. M. Derks, F. P. J. T. Rutjes, J. Roithová, Chem.-Meth. 2021, 1, 430-437.
F. Lanucara, S. W. Holman, C. J. Gray, C. E. Eyers, Nat. Chem. 2014, 6, 281-294.
V. Gabelica, E. Marklund, Curr. Opin. Chem. Biol. 2018, 42, 51-59.
V. Gabelica, A. A. Shvartsburg, C. Afonso, P. Barran, J. L. P. Benesch, C. Bleiholder, M. T. Bowers, A. Bilbao, M. F. Bush, J. L. Campbell, I. D. G. Campuzano, T. Causon, B. H. Clowers, C. S. Creaser, E. De Pauw, J. Far, F. Fernandez-Lima, J. C. Fjeldsted, K. Giles, M. Groessl, C. J. Hogan, Jr., S. Hann, H. I. Kim, R. T. Kurulugama, J. C. May, J. A. McLean, K. Pagel, K. Richardson, M. E. Ridgeway, F. Rosu, F. Sobott, K. Thalassinos, S. J. Valentine, T. Wyttenbach, Mass Spectrom. Rev. 2019, 38, 291-320.
A. E. Kellie, D. G. O′Sullivan, P. W. Sadler, J. Chem. Soc. 1956, 3792-3796.
A. H. Beckett, R. W. Daisley, J. Walker, Tetrahedron. 1968, 24, 6093-6109.
J. M. Rodgers, R. M. Abaskharon, B. Ding, J. Chen, W. Zhang, F. Gai, Phys. Chem. Chem. Phys. 2017, 19, 16144-16150.
L. Marek, J. Vana, J. Svoboda, J. Hanusek, Beil. J. Org. Chem. 2023, 19, 808-819.
A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377.
A. D. McLean, G. S. Chandler, J. Chem. Phys. 1980, 72, 5639-5648.
S. Grimme, S. Ehrlich, L. Goerigk, J. Comput. Chem. 2011, 32, 1456-1465.
e. a. M. J. Frisch, Gaussian 16, Gaussian 16, 2016.
G. T. Thomas, S. Donnecke, I. C. Chagunda, J. S. McIndoe, Chem.-Meth. 2022, 2(1), e202100068.
G. L. Tripodi, M. M. J. Dekker, J. Roithová, L. Que, Jr., Angew. Chem. Int. Ed. 2021, 60, 7126-7131.
G. R. Fulmer, A. J. M. Miller, N. H. Sherden, H. E. Gottlieb, A. Nudelman, B. M. Stoltz, J. E. Bercaw, K. I. Goldberg, Organometallics. 2010, 29, 2176-2179.
