Strong influence of intramolecular Si...O proximity on reactivity:
systematic molecular structure, solvolysis, and mechanistic study of cyclic
N-trimethylsilyl carboxamide derivatives
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Roland Szalay , Veronika Harmat , János Eőri , Gábor Pongor
Institute of Chemistry, Eötvös Loránd University, Budapest
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MTA-ELTE Protein Modeling Research Group, Budapest
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Dedicated to Dezső Knausz for his 80 birthday
Highlights
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Wide range of reactivity in alcohol-induced protodesilylation
Good correlation between reactivity and the Si...O proximity
Two plausible concurrent reaction pathways
Noteworthy XRD structural features of silylated phthalimides
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Reviews: (a) El Gihani MT, Heaney H. Synthesis. 1998; 357-375. (b) van Look G, Simchen G, Heberle J.
Silylating Agents, Fluka Chemie AG: Buchs, Switzerland, 1995. (c) Wuts, P. G. M. Greene’s protective groups
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in organic synthesis, John Wiley & Sons, Inc., Hoboken: New Jersey, 5 ed., 2014.
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Some representative examples: (a) Schettgen T, Dewes P, Kraus T. Anal Bioanal Chem. 2016; 408: 5467-5478.
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b) Molnar B, Fodor B, Boldizsar I, Molnar-Perl I. J Chromatogr, A. 2016; 1440: 172-178. (c) Manzo V, Ulisse
K, Rodriguez I, Pereira E, Richter P. Anal Chim Acta. 2015; 889: 130-137. (d) Raeppel C, Fabritius M, Nief M,
Appenzeller BMR, Millet M. Talanta. 2014; 121: 24-29. (e) Cacho JI, Campillo N, Vinas P, Hernandez-Cordoba
M. J Chromatogr, A. 2012; 1247: 146-153. (f) Kovacs A, Mortl M, Kende A. Microchem J. 2011; 99: 125-131.
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Some representative examples: (a) Homerin G, Baudelet D, Dufrenoy P, Rigo B, Lipka E, Dezitter X, Furman
C, Millet R, Ghinet A. Tetrahedron Lett. 2016; 57: 1165-1170. (b) Liu GJ, Zhang XT, Xing GW. Chem
Commun. 2015; 51: 12803-12806. (c) Wahler K, Ludewig A, Szabo P, Harms K, Meggers E. Eur J Inorg Chem.
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014; 807-811. (d) Blanck S, Geisselbrecht Y, Kraling K, Middel S, Mietke T, Harms K, Essen LO, Meggers E.
Dalton Trans. 2012; 41: 9337-9348. (e) Kardon F, Moertl M, Csampai A, Ujszaszy K, Knausz D. Synth
Commun. 2011; 41: 914-924. (f) Trost BM, Zhang T. Angew Chem, Int Ed. 2008; 47: 3759-3761.
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Volz N, Clayden J. Angew Chem, Int Ed. 2011; 50: 12148-12155.
Szalay R. personal note.
Reviews: (a) Chuit C, Corriu RJP, Reye C, Young JC. Chem Rev. 1993; 93: 1371-1448. (b) Wagler, J.; Bohme,
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U.; Kroke, E. In Functional Molecular Silicon Compounds I: Regular Oxidation States; Scheschkewitz, D., Ed.;
Springer: New York, 2014, pp 29-105. Some representative examples: (c) Nikolin AA, Kramarova EP, Shipov
AG, Baukov YJ,Negrebetsky VV, Arkhipov DE, Korlyukov AA, Lagunin AA, Bylikin SY, Bassindale AR,
Taylor PG. Rsc Adv. 2016; 6: 75315-75327. (d) Steinhauer S, Stammler H-G, Neumann B, Ignat'ev N, Hoge B.
Angew Chem, Int Ed. 2014; 53: 562-564. (e) Azhakar R, Ghadwal RS, Roesky HW, Granitzka M, Stalke D.
Organometallics. 2012; 31: 5506-5510. (f) Metz S, Theis B, Burschka C, Tacke R. Chem—Eur J. 2010; 16:
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844-6856. (g) Holloczki O, Nyulaszi L. Organometallics. 2009; 28: 4159-4164.
Klebe JF. Acc Chem Res. 1970; 3, 9: 299-305.
Lane TH, Frye CL. J Org Chem 1978; 43: 4890-4891.
Szalay R, Pongor G, Harmat V, Bocskei Z, Knausz D. J Organomet Chem. 2005; 690: 1498-1506.
Pongor G, Kolos Z, Szalay R, Knausz D. J Mol Struct-THEOCHEM. 2005; 714: 87-97.
Hua DH, Miao SW, Bharathi SN, Katsuhira T, Bravo AA. J Org Chem. 1990; 55: 3682-3684.
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