Iridium catalyzed cycloaddition reactions

1. Iridium catalyzed cycloaddition reactions 郭蕊 2011.5.16

2. Introduction • Process in cyclosation • Conclusion

3. Transfer hydrogenation and dehydrogenation Crabtree, R. H.: et al.. J. Organomet. Chem. 1977, 141, 205 Crabtree, R. Acc. Chem. Res.1979, 12, 331 Stork, G.; et al. J. Am. Chem. Soc. 1983, 105, 1072 Pfaltz, A. et al. Angew. Chem. Int. Ed.1998, 37, 2897. Pfaltz, A.;et al. Adv. Synth. Catal. 2003, 345, 33. Pfaltz, A. et al. Science,2006, 311, 642

4. Allylic substitution Callman, J. P. et al. Inorg. Chem. 1968, 7, 1298. Takeuchi, R.; et al. Angew. Chem., Int. Ed. 1997, 36, 263.; J. Am. Chem. Soc. 1998, 120, 8647.;Polyhedron2000, 19, 557. Helmchen, G.et al. Tetrahedron Lett. 1997, 38, 8025.

5. Alkynylation Carreira, E. M. et al. Org. Lett. 2001, 3, 4319, Synthesis2004, 1497. Ishii, Y. Chem. Commun. 2004, 1638.

6. Aldol and Related Reactions Matsuda, I.; Tetrahedron Lett. 2000, 41, 1405. Tetrahedron Lett. 2000, 41, 1409. J. Am. Chem. Soc. 2002, 124, 9072.

7. cyclization the general mechanism for ransition metal-catalysed cyclization P. Andrew Evans, et al. Chem Soc. Rev. 2010, 39, 2791

8. 1. [2+2+2] 1.1 Alkyne cyclotrimerisation W. Reppe and W. J. Schweckendiek, Justus Liebigs Ann. Chem.,1948, 560, 104 I. P. Rothwell, et al. Organometallics, 1993,12, 2911. J. Am. Chem. SOC., 1993, 4

9. ligand-controlled iridium-catalysed [2+2+2] carbocyclisation reaction R. Takeuchi, et al. Org. Lett., 2003, 5, 3659

10. 1.2 Two alkynes/diynes with an alkene/alkyne W. Reppe and W. J. Schweckendiek, Justus Liebigs Ann. Chem.,1948, 560, 104 I. P. Rothwell, J. Am. Chem. Soc., 1993,115,1581.

11. Takeuchi, R.; Tanaka, S.; Nakaya, Y. Tetrahedron Lett. 2001, 42, 2991.

12. Org. Lett., 2005,1711

13. Intermolecuar reaction of diynes and monoalkynes a 0.5 mol% catalyst Shibata,T. et al. J. Am．Chem．Soc．2004．126,8382

14. 2. [2+2+1](Pauson-Khand reaction) 2.1 Alkene-alkyne Catalytic enantioselective cobonylation coupling of compound 1 Shibata, T.; Takagi, K. J. Am. Chem. Soc. 2000, 122, 9852.

15. 2.2 alkyne-alkyne/allene Shibata，T．et al. Org．Lett．2001，3，1217 75% when 20kpa CO Shibata，T．et al. Synlett 2003．573．

16. 3. Miscellaneous Reactions 3.1 Enantioselective 1,3-Dipolar Cycloaddition of Nitrones to Methacrolein Daniel Carmona; et al. J. Am．Chem．Soc．2005．127,13386．

17. 3.2 Annulation of 1,3-Dienes with 2-Formylphenylboronic Acid Nishimura, T.;et al.. J. Am. Chem. Soc. 2007,129, 7506.

18. 3.3 [4+2] Shibata, T .;et al. synlett, 2002, 1681 ee up to 95% Shibata, T.; et al.. Synlett2008, 765.

19. 5. carbonylative [5+1] cycloaddition of an allenylcyclopropane Murakami, M.; J. Org. Chem. 1998, 63, 4.

20. cycloisomerization Chatani, N.; Inoue, H.; Morimoto, T.; Muto, T.; Murai, S. J. Org. Chem. 2001, 66, 4433.

21. subsequent cycloisomerization/Diels–Alder reaction/dehydrogenative aromatization 35%-74% Yamamoto, Y.; et al.. J.Am. Chem. Soc. 2005, 127, 10804.

22. From enynes to cyclopropanes Shibata, T.; et al. Tetrahedron 2005, 38, 9018.

23. Iridium-Catalyzed Reaction of Aroyl Chlorides with Internal Alkynes Yasukawa, T.; Satoh, T.; Miura, M.; Nomura, M. J. Am. Chem. Soc. 2002, 124, 12680.

24. Conclusions In most of the cases, the catalytic cycle is Ir(+1) ↔ Ir(+3). The substrate oxidatively adds to Ir(+1) to give Ir(+3). The bond-forming reaction occurs with Ir(+3). The product is then reductively eliminated from Ir(+3) to regenerate Ir(+1). To develop new catalytic reactions, another catalytic cycle needs to be explored.Considering that Ir(+5) has seven coordination sites, the catalytic cycle Ir(+3) ↔ Ir(+5) is more challenging