Chiral Cyclopentadienyl Iridium(III) Complexes Promote Enantioselective Cycloisomerizations Giving Fused Cyclopropanes
Dr. Michael Dieckmann
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, 1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa
Search for more papers by this authorYun-Suk Jang
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, 1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa
Search for more papers by this authorCorresponding Author
Prof. Dr. Nicolai Cramer
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, 1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, 1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsaSearch for more papers by this authorDr. Michael Dieckmann
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, 1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa
Search for more papers by this authorYun-Suk Jang
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, 1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa
Search for more papers by this authorCorresponding Author
Prof. Dr. Nicolai Cramer
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, 1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, 1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsaSearch for more papers by this authorGraphical Abstract
Be selective! A set of chiral CpxIrIII complexes (Cpx=chiral cyclopentadienyl) based on atropchiral cyclopentadienyl ligands are presented. The complexes, in particular the tert-butoxy-substituted derivative (see picture), are shown to promote the asymmetric cycloisomerization of enynes to form fused cyclopropanes with high enantioselectivities.
Abstract
The cyclopentadienyl (Cp) group is a very important ligand for many transition-metal complexes which have been applied in catalysis. The availability of chiral cyclopentadienyl ligands (Cpx) lags behind other ligand classes, thus hampering the investigation of enantioselective processes. We report a library of chiral CpxIrIII complexes equipped with an atropchiral Cp scaffold. A robust complexation procedure reliably provides CpxIrIII complexes with tunable counterions. In a proof-of-concept application, the iodide-bearing members are shown to be highly selective for enyne cycloisomerization reactions. The dehydropiperidine-fused cyclopropane products are formed in good yields and enantioselectivities.
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References
- 1J. Hartwig, Organotransition Metal Chemistry: From Bonding to Catalysis, University Science Books, Sausalito, 2010.
- 2
- 2aR. L. Halterman, K. P. C. Vollhardt, M. E. A. Welker, J. Am. Chem. Soc. 1987, 109, 8105–8107;
- 2bS. L. Colletti, R. L. Halterman, Organometallics 1991, 10, 3438–3448;
- 2cZ. Chen, R. L. Halterman, Synlett 1990, 103–104;
- 2dS. L. Colletti, R. L. Halterman, Tetrahedron Lett. 1989, 30, 3513–3516;
- 2eZ. Li, A. Vasella, Helv. Chim. Acta 1996, 79, 2201–2218;
- 2fR. L. Halterman, L. D. Crow, Tetrahedron Lett. 2003, 44, 2907–2909.
- 3
- 3aR. L. Haltermann, Chem. Rev. 1992, 92, 965–994;
- 3bR. L. Halterman, K. P. C. Vollhardt, Organometallics 1988, 7, 883–892;
- 3cR. L. Halterman, K. P. C. Vollhardt, Tetrahedron Lett. 1986, 27, 1461–1464;
- 3dC. Krüger, R. Goddard, M. Nolte, J. Organomet. Chem. 1993, 459, 107–115;
- 3eA. Gutnov, B. Heller, H.-J. Drexler, A. Spannenberg, G. Oehme, Organometallics 2003, 22, 1550–1553;
- 3fH. Schumann, O. Stenzel, S. Dechert, F. Girgsdies, J. Blum, D. Gelman, R. L. Halterman, Eur. J. Inorg. Chem. 2002, 211–219;
- 3gA. Gutnov, H.-J. Drexler, A. Spannenberg, G. Oehme, B. Heller, Organometallics 2004, 23, 1002–1009;
- 3hG. P. McGlacken, C. T. O′Brien, A. C. Whitwood, I. J. S. Fairlamb, Organometallics 2007, 26, 3722–3728;
- 3iZ. R. Turner, J.-C. Buffet, D. O′Hare, Organometallics 2014, 33, 3891–3903;
- 3jR. Laï, J.-C. Daran, D. Nuel, M. Sanz, N. Summerton, N. Vanthuyne, A. Zaragori-Benedetti, Dalton Trans. 2013, 42, 7980–7990;
- 3kB. Heller, A. Gutnov, C. Fischer, H.-J. Drexler, A. Spannenberg, D. Redkin, C. Sundermann, B. Sundermann, Chem. Eur. J. 2007, 13, 1117–1128;
- 3lA. Gutnov, B. Heller, C. Fischer, H.-J. Drexler, A. Spannenberg, Angew. Chem. Int. Ed. 2004, 43, 3795–3797; Angew. Chem. 2004, 116, 3883–3886.
- 4
- 4aB. Ye, N. Cramer, Science 2012, 338, 504–506;
- 4bB. Ye, N. Cramer, J. Am. Chem. Soc. 2013, 135, 636–639.
- 5
- 5aB. Ye, N. Cramer, Acc. Chem. Res. 2015, 48, 1308–1318;
- 5bB. Ye, N. Cramer, Angew. Chem. Int. Ed. 2014, 53, 7896–7899; Angew. Chem. 2014, 126, 8030–8033;
- 5cM. D. Wodrich, B. Ye, J. F. Gonthier, C. Corminboeuf, N. Cramer, Chem. Eur. J. 2014, 20, 15409–15418;
- 5dB. Ye, P. A. Donets, N. Cramer, Angew. Chem. Int. Ed. 2014, 53, 507–511; Angew. Chem. 2014, 126, 517–521;
- 5eJ. Zheng, S.-L. You, Angew. Chem. Int. Ed. 2014, 53, 13244–13247; Angew. Chem. 2014, 126, 13460–13463;
- 5fJ. Zheng, S.-B. Wang, C. Zheng, S.-L. You, J. Am. Chem. Soc. 2015, 137, 4880–4883;
- 5gB. Ye, N. Cramer, Synlett 2015, 26, 1490–1495;
- 5hG. Y. Song, W. N. O. Wiley, Z. M. Hou, J. Am. Chem. Soc. 2014, 136, 12209–12212.
- 6D. Bellus, S. V. Ley, R. Noyori, M. Regitz, P. J. Reider, E. Schaumann, I. Shinkai, E. J. Thomas, B. M. Trost, in Science of Synthesis—Methods of Molecular Transformations, Vol. 1, (Ed. ), Wiley, New York, 2001.
- 7C. White, A. Yates, P. M. Maitlis, Inorg. Synth. 1992, 29, 228–234.
- 8D. M. Heinekey, J. M. Millar, T. K. Koetzle, N. G. Payne, K. W. Zilm, J. Am. Chem. Soc. 1990, 112, 909–919.
- 9CCDC 1409033 (2 d) and 1410893 (5 g) contain supplementary crystallographic information. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre.
- 10E. Benedetti, A. Simonneau, A. Hours, H. Amouri, A. Penoni, G. Palmisano, M. Malacria, J.-P. Goddard, L. Fensterbank, Adv. Synth. Catal. 2011, 353, 1908–1912.
- 11A. Fürstner, P. W. Davies, Angew. Chem. Int. Ed. 2007, 46, 3410–3449; Angew. Chem. 2007, 119, 3478–3519.
- 12For reviews, see:
- 12aI. D. G. Watson, F. D. Toste, Chem. Sci. 2012, 3, 2899–2919;
- 12bL. Zhang, J. Sun, S. A. Kozmin, Adv. Synth. Catal. 2006, 348, 2271–2296;
- 12cR. Dorel, A. M. Echavarren, J. Org. Chem. 2015, DOI: 10.1021/acs.joc.5b01106.
- 13For examples with AuI and PtII, see:
- 13aA. Fürstner, F. Stelzer, H. Szillat, J. Am. Chem. Soc. 2001, 123, 11863–11869;
- 13bF. Schröder, C. Tugny, E. Salanouve, H. Clavier, L. Giordano, D. Moraleda, Y. Gimbert, V. Mouriès-Mansuy, J.-P. Goddard, L. Fensterbank, Organometallics 2014, 33, 4051–4056;
- 13cD.-H. Zhang, Y. Wei, M. Shi, Chem. Eur. J. 2012, 18, 7026–7029;
- 13dJ. B. Xia, W.-B. Liu, T.-M. Wang, S.-L. You, Chem. Eur. J. 2010, 16, 6442–6446;
- 13eS. Anjum, J. Marco-Contelles, Tetrahedron 2005, 61, 4793–4803;
- 13fJ. Blum, H. Beer-Kraft, Y. Badrieh, J. Org. Chem. 1995, 60, 5567–5569;
- 13gK. Fourmy, S. Mallet-Ladeira, O. Dechy-Cabaret, M. Gouygou, Dalton Trans. 2014, 43, 6728–6734;
- 13hE. Soriano, P. Ballesteros, J. Marco-Contelles, J. Org. Chem. 2004, 69, 8018–8023;
- 13iN. M. Groome, E. E. Elboray, M. W. Inman, H. A. Dondas, R. M. Phillips, C. Kilner, R. Grigg, Chem. Eur. J. 2013, 19, 2180–2184.
- 14For example with further metals, see:
- 14aS. Son, S. Y. Kim, ChemistryOpen 2012, 1, 169–172;
- 14bK. Ota, S. I. Lee, J.-M. Tang, M. Takachi, H. Nakai, T. Morimoto, H. Sakurai, K. Kataoka, N. Chatani, J. Am. Chem. Soc. 2009, 131, 15203–15211;
- 14cS. Y. Kim, J. Org. Chem. 2010, 75, 1281–1284;
- 14dN. Chatani, H. Inoue, T. Morimoto, T. Muto, S. Murai, J. Org. Chem. 2001, 66, 4433–4436;
- 14eS. M. Stevenson, E. T. Newcomb, E. M. Ferreira, Chem. Commun. 2014, 50, 5239–5241;
- 14fS. H. Sim, J. H. Park, Y. K. Chung, Adv. Synth. Catal. 2010, 352, 317–322;
- 14gH. M. Oh, J. E. Park, J. Kim, J. H. Kim, Y. K. Kang, Y. K. Chung, Chem. Eur. J. 2014, 20, 9024–9036;
- 14hJ. Böhmer, R. Grigg, J. D. Marchbank, Chem. Commun. 2002, 768–769.
- 15
- 15aT. Shibata, Y. Kobayashi, S. Maekawa, N. Toshida, K. Takagi, Tetrahedron 2005, 61, 9018–9024;
- 15bM. Barbazanges, M. Augé, J. Moussa, H. Amouri, C. Aubert, C. Desmartes, L. Fensterbank, V. Gandon, M. Malacria, C. Ollivier, Chem. Eur. J. 2011, 17, 13789–13794.
- 16
- 16aA. Pradal, C.-M. Chao, P. Y. Toullec, V. Michelet, Beilstein J. Org. Chem. 2011, 7, 1021–1029;
- 16bK. Yavari, P. Aillard, Y. Zhang, F. Nutter, P. Retailleau, A. Voituriez, A. Marinetti, Angew. Chem. Int. Ed. 2014, 53, 861–865; Angew. Chem. 2014, 126, 880–884;
- 16cP. Pérez-Galán, E. Herrero-Gómez, D. T. Hog, N. J. A. Martin, F. Maseras, A. M. Echavarren, Chem. Sci. 2011, 2, 141–149;
- 16dH. Teller, M. Corbet, L. Mantilli, G. Gopakumar, R. Goddard, W. Thiel, A. Fürstner, J. Am. Chem. Soc. 2012, 134, 15331–15342;
- 16eW. Wang, J. Yang, F. Wang, M. Shi, Organometallics 2011, 30, 3859–3869.
- 17
- 17aD. Brissy, M. Skander, H. Jullien, P. Retailleau, A. Marinetti, Org. Lett. 2009, 11, 2137–2139;
- 17bD. Brissy, M. Skander, P. Retailleau, G. Frison, A. Marinetti, Organometallics 2009, 28, 140–151.
- 18
- 18aT. Nishimura, Y. Maeda, T. Hayashi, Org. Lett. 2011, 13, 3674–3677;
- 18bT. Nishimura, Y. Takiguchi, Y. Maeda, T. Hayashi, Adv. Synth. Catal. 2013, 355, 1374–1382;
- 18cK. Matsutomi, K. Noguchi, K. Tanaka, J. Am. Chem. Soc. 2014, 136, 7626–7630.
- 19Terminal alkyne substrates in Au catalysis typically furnish 5-exo-dig products (Refs. [16c], [16e]). A single example of 6-endo-dig cyclization gives 23 % yield and 22 % ee (Ref. [16a]).
- 20V. S. Sridevi, W. Y. Fan, W. K. Leong, Organometallics 2007, 26, 1173–1177.
- 21See the Supporting Information for details.
