Synthesis of Chiral Indenylcobalt(I) Complexes and Their Evaluation in Asymmetric [2+2+2] Cycloaddition Reactions

Dedicated to Prof. Dr. Detlef Heller on the occasion of his 60^th birthday

Abstract

The syntheses of two new indenyl-based cobalt(I) complexes were reported and their properties as catalysts in asymmetric cyclotrimerizations evaluated. While one complex was synthesized from a functionalized BINOL derivative by cross-coupling with 2-indenylboronate, the other complex was derived from a known chiral indenyl cobalt(I) complex by exchange of COD for two phosphite ligands, delivering the first chiral indenyl cobalt(I) complex, which can easily be activated thermally. The prepared complexes were tested in asymmetric cyclization reactions of triynes as well as diynes with nitriles to deliver chiral triaryls and heterobiaryls, respectively. While the BINOL-based precatalysts promoted the cyclizations in good yield without selectivity, the bisphosphite cobalt(I) complex induces chirality with up to 80% ee under photochemical as well as under thermal conditions.

Key words

cobalt - asymmetric catalysis - [2+2+2] cycloaddition - indenyl complexes - phosphites - metal complexation

• References

• 1 Current address: Laboratory of Inorganic Chemistry, ETH Zürich, Vladimir-Prelog-Weg 3, 8093 Zurich, Switzerland.
• 2 Additional address since November 1, 2015: Johannes Kepler University Linz, Institute for Catalysis, Altenberger Str. 69, 4040 Linz, Austria.
• 3 Halterman RL. Chem. Rev. 1992; 92: 965
• 4 Schumann H, Stenzel O, Dechert S, Halterman RL. Organometallics 2001; 20: 1983 ; and references cited therein

For selected examples for Ti, see:
• 5a Cesarotti E, Kagan HB, Goddard R, Krüger C. J. Organomet. Chem. 1978; 162: 297
• 5b Couturier S, Tainturier G, Gautheron B. J. Organomet. Chem. 1980; 195: 291
• 5c Colletti SL, Halterman RL. Tetrahedron Lett. 1989; 30: 3513
• 5d Colletti SL, Halterman RL. Organometallics 1991; 10: 3438
• 5e Halterman RL, Vollhardt KP. C. Organometallics 1988; 7: 88

For Zr, see:
• 6a Zhang Y, Liao S, Xu Y, Chen S. J. Organomet. Chem. 1990; 382: 69
• 6b Erker G. J. Organomet. Chem. 1990; 400: 185
• 6c Erker G, van derZeijden AA. H. Angew. Chem., Int. Ed. Engl. 1990; 29: 512 ; Angew. Chem. 1990, 102, 543
• 6d Erker G. Pure Appl. Chem. 1991; 63: 797

Selected examples for Ru:
• 7a Cesarotti E, Ciani G, Sironi A. J. Organomet. Chem. 1981; 216: 87
• 7b Lindsay C, Cesarotti E, Adams H, Bailey NA, White C. Organometallics 1990; 9: 2594
• 8 Selected example for Rh: Schofield PA, Adams H, Bailey NA, Cesarotti E, White C. J. Organomet. Chem. 1991; 412: 273
• 9a Halterman RL, Vollhardt KP. C. Tetrahedron Lett. 1986; 27: 1461
• 9b Paquette LA, Moriarty KJ, McKinney JA, Rogers RD. Organometallics 1989; 8: 1707
• 9c McLaughlin ML, McKinney JA, Paquette LA. Tetrahedron Lett. 1986; 27: 5595
• 9d Paquette LA, McKinney JA, McLaughlin ML, Rheingold AL. Tetrahedron Lett. 1986; 27: 5599
• 10a Hofmann W, Buchner W, Werner H. Angew. Chem., Int. Ed. Engl. 1977; 16: 795 ; Angew. Chem. 1977, 89, 836
• 10b Werner H, Hofmann W. Chem. Ber. 1981; 114: 2681
• 11 Ye B, Cramer N. Acc. Chem. Res. 2015; 48: 1308
• 12 Dieckmann M, Jang Y.-S, Cramer N. Angew. Chem. Int. Ed. 2015; 54: 12149 ; Angew. Chem. 2015, 127, 12317
• 13a Ye B, Cramer N. Science 2012; 338: 504
• 13b Ye B, Cramer N. J. Am. Chem. Soc. 2013; 135: 636
• 14 Gutnov A, Heller B, Drexler H.-J, Spannenberg A, Oehme G. Organometallics 2003; 22: 1550
• 15 Gutnov A, Drexler H.-J, Spannenberg A, Oehme G, Heller B. Organometallics 2004; 23: 1002
• 16a Gutnov A, Heller B, Fischer C, Drexler H.-J, Spannenberg A, Sundermann B, Sundermann C. Angew. Chem. Int. Ed. 2004; 43: 3795 ; Angew. Chem. 2004, 116, 3883
• 16b Hapke M, Kral K, Fischer C, Spannenberg A, Gutnov A, Redkin D, Heller B. J. Org. Chem. 2010; 75: 3993
• 17 Weding N, Hapke M. Chem Soc. Rev. 2011; 40: 4525
• 18a Shibata T, Fujimoto T, Yokota K, Takagi K. J. Am. Chem. Soc. 2004; 126: 8382
• 18b Tanaka K, Nishida G, Wada A, Noguchi K. Angew. Chem. Int. Ed. 2004; 43: 6510 ; Angew. Chem. 2004, 116, 6672
• 19a Tanaka K In Transition-Metal-Mediated Aromatic Ring Construction. Tanaka K. Wiley; Hoboken: 2013: 127
• 19b Takeuchi R In Transition-Metal-Mediated Aromatic Ring Construction . Tanaka K. Wiley; Hoboken: 2013: 161
• 20 Heller B, Sundermann B, Fischer C, You J, Chen W, Drexler H.-J, Knochel P, Bonrath W, Gutnov A. J. Org. Chem. 2003; 68: 9221
• 21 Fischer F, Jungk P, Weding N, Spannenberg A, Ott H, Hapke M. Eur. J. Org. Chem. 2012; 5828
• 22 Hapke M, Weding N, Spannenberg A. Organometallics 2010; 29: 4298
• 23 Thiel I, Jiao H, Spannenberg A, Hapke M. Chem. Eur. J. 2013; 19: 2548
• 24 Thiel I, Spannenberg A, Hapke M. ChemCatChem 2013; 5: 2865
• 25a Baker RW, Wallace BJ. Chem. Commun. 1999; 1405
• 25b Schumann H, Stenzel O, Dechert S, Girgsdies F, Halterman RL. Organometallics 2001; 20: 2215
• 25c Schumann H, Stenzel O, Dechert S, Girgsdies F, Halterman RL. Organometallics 2001; 20: 5360
• 25d Schumann H, Stenzel O, Dechert S, Girgsdies F, Blum J, Gelman D, Halterman RL. Eur. J. Inorg. Chem. 2002; 211
• 25e Kataoka Y, Shimada K, Goi T, Yamagata T, Mashima K, Tani K. Inorg. Chim. Acta 2004; 357: 2965
• 25f Vitanove DV, Hampel F, Haltzsch KC. J. Organomet. Chem. 2007; 692: 4690
• 25g Baker RW, Radzey H, Lucas NT, Turner P. Organometallics 2012; 31: 5622
• 25h Baker RW, Turner P, Luck IJ. Organometallics 2015; 34: 1751
• 26 Yang X.-W, Sheng J.-H, Da C.-S, Wang H.-S, Su W, Wang R, Chan AS. C. J. Org. Chem. 2000; 65: 295
• 27a Ma L, Jin R.-Z, Lü G.-H, Bian Z, Ding M.-X, Gao L.-X. Synthesis 2007; 2461
• 27b Ooi T, Kameda M, Maruoka K. J. Am. Chem. Soc. 2003; 125: 5139
• 28a Jin L, Huang Y, Jing H, Chang T, Yan P. Tetrahedron: Asymmetry 2008; 19: 1947
• 28b Taniguchi T, Fukuba T.-a, Nakatsuka S, Hayase S, Kawatsura M, Uno H, Itoh T. J. Org. Chem. 2008; 73: 3875
• 28c Nishioka Y, Uchida T, Katsuki T. Angew. Chem. Int. Ed. 2013; 52: 1739 ; Angew. Chem. 2013, 125, 1783
• 29 Lipshutz BH, Blomgren PA. Org. Lett. 2001; 3: 1869
• 30 For achiral cyclizations, see: Jungk P, Fischer F, Thiel I, Hapke M. J. Org. Chem. 2015; 80: 9781
• 31 Harada T, Kanda K. Org. Lett. 2006; 8: 3817
• 32 Li Y, Li Q. Org. Lett. 2012; 14: 4362
• 33 Shibata T, Tsuchikama K, Otsuka M. Tetrahedron: Asymmetry 2006; 17: 614