1. Palladium-catalysed reactions involving isocyanides Reporter: Xinzheng Chen Supervisor: Prof. David Zhigang Wang 2013-12-19

2. 2 Content 1. Introduction 2. Isocyanide insertions into the palladium–carbon bond 3. Applications in organic synthesis 4. Summary

3. 3 Content 1. Introduction 2. Isocyanide insertions into the palladium–carbon bond 3. Applications in organic synthesis 4. Summary

4. 4 Structure and physical properties Introduction The C-N distance in isocyanides is very short, 1.158 Å in methyl isocyanide. The C-N-C angles are near 180°. Isocyanides are described by two resonance structures, one with a triple bond between the nitrogen and the carbon and one with a double bond between. Isocyanides exhibit a strong absorption in their IR spectra in the range: 2165–2110 cm -1. P. Fleurat-Lessard et al., New J. Chem., 2012, 36, 1137-1140. R. W. Stephany et al., Organic Magnetic Resonance, 1974, 6 (1): 45-47.

5. 5 Introduction Synthesis of isocyanides The first isocyanide, allyl isocyanide, was reported in 1859 by the chemist Lieke from the reaction of allyl iodide and silver cyanide. Normally the alkylation of an alkali metal cyanide gives a nitrile, but the silver ion protects the carbon end of the cyanide. W. Lieke, Justus Liebigs Annalen der Chemie, 1859, 112 (3): 316–321. J. E. Scott et al., Org. Synth., 1966, 46, 75. R. Meyr et al., Angewandte Chemie, 1958, 70, 702–703. A. W. Hofmann, Ann., 1868, 146, 107. A. W. Hofmann, Ber., 1870, 3, 767.

6. 6 Content 1. Introduction 2. Isocyanide insertions into the palladium–carbon bond 3. Applications in organic synthesis 4. Summary

7. 7 Isocyanide insertions into the palladium–carbon bond R. J. Whitby et al., Angew. Chem. Int. Ed., 2000, 39, 4156–4158.

8. 8 Isocyanide insertions into the palladium–carbon bond Insertion of 2,6-dimethylphenyl isocyanide to Pd–C bond Cyclisation reactions involving isocyanates and isothiocyanates R. Vilar et al., Organometallics, 2002, 21, 4799–4807. R. Vilar et al., Organometallics, 2003, 22, 4511–4521.

9. 9 Isocyanide insertions into the palladium–carbon bond Insertion of tert-butyl isocyanide to Pd–C bond of Pd complex with NHC ligand Reversible insertion of isocyanide to Pd–C bond R. F. Jordan et al., Organometallics, 2011, 30, 4632–4642. J. Vicente et al., Organometallics, 2004, 23, 1292–1304.

10. 10 Content 1. Introduction 2. Isocyanide insertions into the palladium–carbon bond 3. Applications in organic synthesis 4. Summary

11. 11 Applications in organic synthesis Synthesis of vinyl compounds Intramolecular insertion of isocyanides R. J. Whitby et al., Tetrahedron Lett., 2004, 45, 6991–6994. R. J. Whitby et al., Tetrahedron Lett., 2004, 45, 6995–6996.

12. 12 Applications in organic synthesis Synthesis of isocoumarin and phthalide compoundsSynthesis of amides S.-J. Ji et al., J. Org. Chem., 2012, 77, 10321–10328. H. Jiang et al., Org. Lett., 2011, 13, 1028–1031.

13. 13 Applications in organic synthesis J. Vicente et al., Organometallics, 2012, 31, 3361–3372. P. J. Boissarie et al., Org. Lett., 2011, 13, 6256–6259. Exploration of isocyanide insertion reactionsSynthesis of substituted oxazoline, benzoxazole and benzothiazole

14. 14 Applications in organic synthesis Synthesis of iminopyrrolone H. Jiang et al., Adv. Synth. Catal., 2012, 354, 2288–2300.

15. 15 Applications in organic synthesis Synthesis of aminophthalazinonesSynthesis of quinazolines R. V. A. Orru et al., Org. Lett., 2011, 13, 6496–6499. R. V. A. Orru et al., Chem.–Eur. J., 2011, 17, 15037–15044.

16. 16 Applications in organic synthesis J. Wu et al., Chem. Commun., 2012, 48, 2903–2905. J. Wu et al., Chem. Commun., 2012, 48, 3836–3838. Synthesis of complex quinazolines

17. 17 Applications in organic synthesis Synthesis of indole using functionalised isocyanide S. Takahashi et al., Tetrahedron Lett., 2002, 43, 6197–6199.

18. 18 Applications in organic synthesis Y. Yamamoto et al., J. Am. Chem. Soc., 2002, 124, 11940–11945. R. V. A. Orru et al., Angew. Chem., Int. Ed., 2012, 51, 13058–13061. Synthesis of indoleSynthesis of heterocycles using isocyanide 2

19. 19 Applications in organic synthesis Synthesis ofa,b-unsaturated cyclic imine T. Hayashi et al., Chem. Lett., 2009, 38, 204–205.

20. 20 Applications in organic synthesis M. Murakami et al., Org. Lett., 2011, 13, 1429–1431. Q. Zhu et al., Org. Lett., 2011, 13, 4604–4607. Synthesis of isoindolinone and thiaisoindolinoneSynthesis of quinazolines using C–H activation

21. 21 Applications in organic synthesis Synthesis of amide using C–H activation Q. Zhu et al., Chem. Commun., 2012, 48, 3772–3774.

22. 22 Applications in organic synthesis Synthesis of natural product like analogues W. Du et al., Org. Lett., 2002, 4, 3215–3218.

23. 23 Content 1. Introduction 2. Isocyanide insertions into the palladium–carbon bond 3. Applications in organic synthesis 4. Summary

24. 24 Summary

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