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New Developments in Pd(II)-Catalysed Cyclisations of Aminoalkenitols Dr. Peter Szolcsányi Department of Organic Chemistry Slovak University of Technology.

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Presentation on theme: "New Developments in Pd(II)-Catalysed Cyclisations of Aminoalkenitols Dr. Peter Szolcsányi Department of Organic Chemistry Slovak University of Technology."— Presentation transcript:

1 New Developments in Pd(II)-Catalysed Cyclisations of Aminoalkenitols Dr. Peter Szolcsányi Department of Organic Chemistry Slovak University of Technology Bratislava, Slovak Republic

2 Pd(II)-Catalysed chlorocyclisation and N,O-bicyclisation of polyhydroxylated aminoalkenitols

3 Synthetic versatility of chloromethyl piperidines

4 Where did the idea come from ? P. Szolcsányi et al.: Tetrahedron: Asymmetry 2000, 11, 2579-2597.

5 Known precedents of Pd(II)/CuCl 2 -catalysed chloroaminocyclisation M. Wada, H. Aiura, K. Akiba: Heterocycles 1987, 26, 929-934. A. Lei, X. Lu, G. Liu: Tetrahedron Lett. 2004, 45, 1785-1788.

6 Preparation of substrates - D-gluco compound

7 Preparation of substrates - D-galacto compound

8 Pd(II)/CuCl 2 -catalysed chlorocyclisation-D-gluco serie EntrySolventTime & Temperature Isolated yield (after FLC) HPLC ratio of L-ido / D-gluco (d.e.) 1AcOH48 hrs, 23 o C70%19 / 1 (90%) 2DMF24 hrs, 30 o C21% 8 / 1 (82%) 3CH 2 Cl 2 24 hrs, 30 o C65% 6 / 1 (71%) 4THF24 hrs, 30 o C60%6 / 1 (71%) 5MeOH24 hrs, 23°C59%5 / 1 (67%) 6Toluene48 hrs, 30 o C56% 3 / 1 (33%)

9 Pd(II)/CuCl 2 -catalysed chlorocyclisation-D-galacto serie EntrySolventCatalyst & Additive(s) Time & Temperature Chlorides/bicycle (yield after FLC) HPLC ratio of L-altro/D-gala (d.e.) 1AcOH0.1 eq. PdCl 2, 3 eq. CuCl 2, 3 eq. AcONa24 hrs, 25 o C28% / 49%19 / 1 (90%) 2DMF- detto -19 hrs, 25 o C53% / 11%15 / 1 (88%) 3CH 2 Cl 2 - detto -24 hrs, 29 o C36% / 8% 5 / 1 (67%) 4THF- detto -24 hrs, 25 o C54% / 10%2 / 1 (33%) 5Toluene- detto -24 hrs, 29 o C43% / 9%1 / 2 (33%) 6MeOH- detto -24 hrs, 25 o C32% / 7%1 / 3 (50%) 7AcOH0.1 eq. PdCl 2, 2 eq. CuCl 2, 2 eq. AcONa48 hrs, 30 o C35% / 52%19 / 1 (90%) 8AcOH0.1 eq. PdCl 2, 1 eq. CuCl 2, 1 eq. AcONa48 hrs, 28 o C25% / 48%19 / 1 (90%) 9AcOH0.1 eq. PdCl 2, 3 eq. CuCl 2 24 hrs, 30 o C27% / 50%19 / 1 (90%) 10AcOH1 eq. PdCl 2, 3 eq. AcONa96 hrs, 28 o C0% / 0%- 11AcOH0.1 eq. Pd(OAc) 2, 2 eq. BQ, 3 eq. AcONa24 hrs, 30 o C- / 0%-

10 Mechanistic proposal of the Pd(II)/CuCl 2 -catalysed chloroaminocyclisation and bicyclisation

11 Synthesis of new analogues of iminoalditols H. Takahata, Y. Banba, H. Ouchi, H. Nemoto: Org. Lett. 2003, 5, 2527-2529.

12 New type of the Pd(II)/CuCl 2 -catalysed bicyclisation ??? Analogous to: T. M. Cokley et al.: Tetrahedron Lett. 1996, 37, 1905-1908. Preparation of model substrate for the bicyclisation

13 Model screening of Pd(II)/CuCl 2 -catalysed bicyclisation EntrySolventCatalyst & Additive(s)Time & TemperatureYield after FLC 1AcOH0.1 eq. PdCl 2, 3 eq. CuCl 2, 3 eq. AcONa 20°C, 24 hrs 45% 2AcOH0.2 eq. Pd(OAc) 2, 3 eq. Cu(OAc) 2 30°C, 48 hrs Complex mixture 3THF0.2 eq. PdCl 2, 1.1 eq. BQ, 2 eq. LiCl 45°C, 48 hrs Complex mixture 4AcOH0.1 eq. PdCl 2, 3 eq. CuCl 2 35°C, 24 hrs 71% 5AcOH0.1 eq. PdCl 2, 2 eq. CuCl 2 40°C, 48 hrs 65% 6AcOH0.1 eq. PdCl 2, 1 eq. CuCl 2 40°C, 48 hrs 74% 7CH 2 Cl 2 0.1 eq. PdCl 2, 2 eq. CuCl 2 35°C, 22 hrs 71% 8THF0.1 eq. PdCl 2, 2 eq. CuCl 2 35°C, 22 hrs 47% 9AcOH0.1 eq. Pd(OAc) 2, 2 eq. CuCl 2 40°C, 12 hrs 64% 10AcOH0.1 eq. PdCl 2 (MeCN) 2, 2 eq. CuCl 2 40°C, 12 hrs 69% 11AcOH1 eq. PdCl 2 40°C, 26 hrs0%

14 Mechanistic proposal of Pd(II)/CuCl 2 -catalysed bicyclisation P. Szolcsányi, T. Gracza: Chem. Commun. 2005, 3948-3950.

15 Acknowledgments Generous supportProf. Dr. Tibor Gracza HPLCDr. Katarína Hroboňová NMRDr. Naďa Prónayová IRMs. Silvia Markusová MALDIDr. Ivan Špánik GrantAPVT-20-000904

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