Regioselectivity in Thermal Rhodium(II)-Catalysed Büchner-Type Reactions of Substituted Aryl Halides: Studies towards the Synthesis of Halide-Substituted Cycloheptatrienes

Abstract

The results of Büchner-type reactions of various substituted aryl halide derivatives with ethyl diazoacetate are presented, together with a discussion of factors affecting the regioselectivity of these processes.

Büchner reaction - regioselectivity - cycloaddition - carbenoids - rearrangement

References and Notes

1a Doyle MP. McKervey MA. Ye T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds   Wiley-Interscience; New York: 1998. 

1b Ye T. Mckervey MA. Chem. Rev.  1994,  94:  1091 

2a Anciaux AJ. Demonceau A. Hubert AJ. Noels AF. Petiniot N. Teyssie P. J. Chem. Soc., Chem. Commun.  1980,  16:  765 

2b Anciaux AJ. Demonceau A. Noels AF. Hubert AJ. Warin R. Teyssie P. J. Org. Chem.  1981,  46:  873 

3a Kürtz L. Czakó B. Strategic Applications of Named Reactions in Organic Synthesis   Elsevier Academic Press; Amsterdam: 2005. 

3b Maguire AR. Buckley NR. O’Leary P. Ferguson G. J. Chem. Soc., Perkin Trans. 1  1998,  24:  4077 

3c Maguire AR. Buckley NR. O’Leary P. Ferguson G. Chem. Commun.  1996,  22:  2595 

3d Kane JL. Shea KM. Crombie AL. Danheiser RL. Org. Lett.  2001,  3:  1081 

3e Frey B. Wells AP. Rogers DH. Mander LN. J. Am. Chem. Soc.  1998,  120:  1914 

See ref. 2a and 2b. See also:

4a Lovely CJ. Browning RG. Badarinarayana V. Dias HVR. Tetrahedron Lett.  2005,  46:  2453 

4b Morilla ME. Diaz-Requejo MM. Belderrain TR. Nicasio MC. Trofimenko S. Perez PJ. Organometallics  2004,  23:  293 

5 See ref. 1a, 2a, and 2b. See also: Gale DM. J. Org. Chem.  1968,  33:  2536 

For the discovery of the antibacterial agent emmacin, see:

6a Wyatt EE. Fergus S. Galloway WRJD. Bender A. Fox DJ. Plowright AT. Jessiman AS. Welch M. Spring DR. Chem. Commun.  2006,  3296 

6b Wyatt EE. Fergus S. Galloway WRJD. Bender A. Thomas GL. Welch M. Loiseleur O. Plowright AT. Spring DR. Chem. Commun.  2008,  4962 

For recent reviews on DOS, see:

6c Schreiber SL. Nature (London)  2009,  457:  153 

6d Galloway WRJD. Isidro-Llobet A. Spring DR. Nat. Commun.  2010,  1:  80 

6e Nielsen E. Schreiber SL. Angew. Chem. Int. Ed.  2008,  47:  48 

6f Galloway WRJD. Bender A. Welch M. Spring DR. Chem. Commun.  2009,  2446 

6g Cordier C. Morton D. Murrison S. Nelson A. O’Leary-Steele C. Nat. Prod. Rep.  2008,  25:  719 

7

A full account of our computational modelling studies on the Büchner reactions described in this paper will be reported in due course.