Silylative Cyclopropanation of Allyl Phosphates with Silylboronates†
Corresponding Author
Dr. Ryo Shintani
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)Search for more papers by this authorRyuhei Fujie
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
Search for more papers by this authorDr. Momotaro Takeda
Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Kyoko Nozaki
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)Search for more papers by this authorCorresponding Author
Dr. Ryo Shintani
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)Search for more papers by this authorRyuhei Fujie
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
Search for more papers by this authorDr. Momotaro Takeda
Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Kyoko Nozaki
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)Search for more papers by this authorSupport has been provided in part by a Grant-in-Aid for Young Scientists (B), the Ministry of Education, Culture, Sports, Science and Technology (Japan), and the Asahi Glass Foundation. M.T. thanks JSPS for a fellowship.
Graphical Abstract
β attack! A potassium-bis(trimethylsilyl)amide-mediated cyclopropanation of allyl phosphates with silylboronates has been developed. Unlike the reported copper-catalyzed allylic substitution reactions, the nucleophile selectively attacks at the β-position of the allylic substrates under the present conditions. The reaction mechanism has also been investigated, thus indicating the involvement of a silylpotassium species as the active nucleophilic component.
Abstract
A potassium-bis(trimethylsilyl)amide-mediated cyclopropanation of allyl phosphates with silylboronates has been developed. Unlike the reported copper-catalyzed allylic substitution reactions, the nucleophile selectively attacks at the β-position of the allylic substrates under the present reaction conditions. The mechanism of this process has also been investigated, thus indicating the involvement of a silylpotassium species as the active nucleophilic component.
Supporting Information
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References
- 1For reviews, see:
- 1aH. Pellissier, Tetrahedron 2008, 64, 7041;
- 1bH. Lebel, J.-F. Marcoux, C. Molinaro, A. B. Charette, Chem. Rev. 2003, 103, 977.
- 2For selected examples, see:
- 2aS. Torii, H. Tanaka, Y. Nagai, Bull. Chem. Soc. Jpn. 1977, 50, 2825;
- 2bR. Verhé, N. De Kimpe, L. De Buyck, D. Courtheyn, L. Van Caenegem, N. Schamp, Bull. Soc. Chim. Belg. 1983, 92, 371;
- 2cM. P. Cooke, Jr., J. Y. Jaw, J. Org. Chem. 1986, 51, 758;
- 2dE. Vilsmaier, R. Adam, C. Tetzlaff, R. Cronauer, Tetrahedron 1989, 45, 3683;
- 2eS. Nakamura, Y. Watanabe, T. Toru, J. Chem. Soc. Perkin Trans. 1 1999, 3403;
- 2fH.-S. Jeon, S. Koo, Tetrahedron Lett. 2004, 45, 7023;
- 2gT. den Hartog, A. Rudolph, B. Marciá, A. J. Minnaard, B. L. Feringa, J. Am. Chem. Soc. 2010, 132, 14349.
- 3
- 3aL. S. Hegedus, W. H. Darlington, C. E. Russell, J. Org. Chem. 1980, 45, 5193;
- 3bH. M. R. Hoffmann, A. R. Otte, A. Wilde, Angew. Chem. 1992, 104, 224; Angew. Chem. Int. Ed. Engl. 1992, 31, 234;
- 3cA. Wilde, A. R. Otte, H. M. R. Hoffmann, J. Chem. Soc. Chem. Commun. 1993, 615;
- 3dA. R. Otte, A. Wilde, H. M. R. Hoffmann, Angew. Chem. 1994, 106, 1352; Angew. Chem. Int. Ed. Engl. 1994, 33, 1280;
- 3eH. M. R. Hoffmann, A. R. Otte, A. Wilde, S. Menzer, D. J. Williams, Angew. Chem. 1995, 107, 73;
10.1002/ange.19951070113 Google ScholarAngew. Chem. Int. Ed. Engl. 1995, 34, 100.
- 4
- 4aM. Formica, A. Musco, R. Pontellini, K. Linn, C. Mealli, J. Organomet. Chem. 1993, 448, C 6;
- 4bA. Satake, T. Nakata, J. Am. Chem. Soc. 1998, 120, 10391;
- 4cA. Satake, H. Koshino, T. Nakata, Chem. Lett. 1999, 49;
- 4dA. Satake, H. Kadohama, H. Koshino, T. Nakata, Tetrahedron Lett. 1999, 40, 3597;
- 4eW. Liu, D. Chen, X.-Z. Zhu, X.-L. Wan, X.-L. Hou, J. Am. Chem. Soc. 2009, 131, 8734.
- 5
- 5aR. Grigg, M. Kordes, Eur. J. Org. Chem. 2001, 707;
- 5bR. Shintani, S. Park, F. Shirozu, M. Murakami, T. Hayashi, J. Am. Chem. Soc. 2008, 130, 16174;
- 5cR. Shintani, T. Tsuji, S. Park, T. Hayashi, J. Am. Chem. Soc. 2010, 132, 7508;
- 5dR. Shintani, K. Moriya, T. Hayashi, Chem. Commun. 2011, 47, 3057;
- 5eR. Shintani, T. Ito, M. Nagamoto, H. Otomo, T. Hayashi, Chem. Commun. 2012, 48, 9936.
- 6R. Shintani, T. Ito, T. Hayashi, Org. Lett. 2012, 14, 2410.
- 7C. Zhong, S. Kunii, Y. Kosaka, M. Sawamura, H. Ito, J. Am. Chem. Soc. 2010, 132, 11440.
- 8A. Kawachi, H. Maeda, H. Nakamura, N. Doi, K. Tamao, J. Am. Chem. Soc. 2001, 123, 3143.
- 9
- 9aL. B. Delvos, D. J. Vyas, M. Oestreich, Angew. Chem. 2013, 125, 4748;
10.1002/ange.201300648 Google ScholarAngew. Chem. Int. Ed. 2013, 52, 4650;
- 9bM. Takeda, R. Shintani, T. Hayashi, J. Org. Chem. 2013, 78, 5007.
- 10For recent reviews on SiB compounds, see:
- 10aM. Oestreich, E. Hartmann, M. Mewald, Chem. Rev. 2013, 113, 402;
- 10bT. Ohmura, M. Suginome, Bull. Chem. Soc. Jpn. 2009, 82, 29.
- 11For pioneering work on the preparation and use of this silylboronate, see:
- 11aM. Suginome, H. Nakamura, Y. Ito, Chem. Commun. 1996, 2777;
- 11bM. Suginome, T. Matsuda, Y. Ito, Organometallics 2000, 19, 4647.
- 12For selected recent examples for the transition-metal-catalyzed reactions using silylboronates, see:
- 12aT. Ohmura, K. Masuda, M. Suginome, J. Am. Chem. Soc. 2008, 130, 1526;
- 12bC. Walter, M. Oestreich, Angew. Chem. 2008, 120, 3878; Angew. Chem. Int. Ed. 2008, 47, 3818;
- 12cK. Lee, A. H. Hoveyda, J. Am. Chem. Soc. 2010, 132, 2898;
- 12dT. Ohmura, K. Oshima, H. Taniguchi, M. Suginome, J. Am. Chem. Soc. 2010, 132, 12194;
- 12eE. Hartmann, M. Oestreich, Angew. Chem. 2010, 122, 6331; Angew. Chem. Int. Ed. 2010, 49, 6195;
- 12fD. J. Vyas, M. Oestreich, Angew. Chem. 2010, 122, 8692;
10.1002/ange.201004658 Google ScholarAngew. Chem. Int. Ed. 2010, 49, 8513;
- 12gP. Wang, X.-L. Yeo, T.-P. Loh, J. Am. Chem. Soc. 2011, 133, 1254;
- 12hK. Oshima, T. Ohmura, M. Suginome, J. Am. Chem. Soc. 2011, 133, 7324;
- 12iC. Kleeberg, M. S. Cheung, Z. Lin, T. B. Marder, J. Am. Chem. Soc. 2011, 133, 19060;
- 12jN. Saito, A. Kobayashi, Y. Sato, Angew. Chem. 2012, 124, 1254; Angew. Chem. Int. Ed. 2012, 51, 1228;
- 12kT. Fujihara, Y. Tani, K. Semba, J. Terao, Y. Tsuji, Angew. Chem. 2012, 124, 11655;
10.1002/ange.201207148 Google ScholarAngew. Chem. Int. Ed. 2012, 51, 11487;
- 12lV. Cirriez, C. Rasson, T. Hermant, J. Petrignet, J. Díaz Álvarez, K. Robeyns, O. Riant, Angew. Chem. 2013, 125, 1829;
10.1002/ange.201209020 Google ScholarAngew. Chem. Int. Ed. 2013, 52, 1785;
- 12mC. Zarate, R. Martin, J. Am. Chem. Soc. 2014, 136, 2236.
- 13For examples of the usage of silylboronates in the absence of transition-metal catalysts, see:
- 13aA. Kawachi, T. Minamimoto, K. Tamao, Chem. Lett. 2001, 1216;
- 13bJ. M. O’Brien, A. H. Hoveyda, J. Am. Chem. Soc. 2011, 133, 7712;
- 13cH. Ito, Y. Horita, E. Yamamoto, Chem. Commun. 2012, 48, 8006;
- 13dE. Yamamoto, K. Izumi, Y. Horita, H. Ito, J. Am. Chem. Soc. 2012, 134, 19997.
- 14Addition of silylboronates to styrenes catalyzed by KOtBu has been reported in Ref. [13c].
- 15ICP-AES analysis of KN(SiMe3)2 (Aldrich, 95 %) showed that detectable trace metals were Na (480 ppm), Mg (2.7 ppm), Ca (5.6 ppm), Fe (0.7 ppm), and Zr (0.2 ppm) where 1 ppm=1×10−6 mg per 1 mg of KN(SiMe3)2.
- 16Notes:
- 16aThe substrates 1 bearing a heteroaryl group such as R=2-furyl or 1-methyl-6-indolyl could not be employed because of their thermal instability.
- 16bThe substrates 1 bearing an alkyl group such as R=n-pentyl were not applicable to the present cyclopropanation, resulting in the exclusive formation of the allylic substitution products 4.
- 17Y. Cui, W. Li, T. Sato, Y. Yamashita, S. Kobayashi, Adv. Synth. Catal. 2013, 355, 1193.
- 18Generation and spectroscopic confirmation of a silyllithium by the reaction of a silylboronate with MeLi or nBuLi have been reported in Ref. [13a]. Similarly, generation of a silylpotassium from a silylboronate and excess KOtBu and a silylmagnesium bromide from a silylboronate and excess MeMgBr have also been suggested (with no spectroscopic evidence) in this paper.
- 19E. Buncel, T. K. Venkatachalam, B. Eliasson, U. Edlund, J. Am. Chem. Soc. 1985, 107, 303.
- 20We currently do not have a good explanation for the origin of the selective nucleophilic attack at the β-position. For relevant examples using silicon nucleophiles, see Refs. [8] and [13c].
- 21For a review, see: G. R. Jones, Y. Landais, Tetrahedron 1996, 52, 7599.
- 22aK. Tamao, N. Ishida, T. Tanaka, M. Kumada, Organometallics 1983, 2, 1694;
- 22bK. Tamao, N. Ishida, J. Organomet. Chem. 1984, 269, C 37;
- 22cK. Tamao, E. Nakajo, Y. Ito, J. Org. Chem. 1987, 52, 4412;
- 22dK. Tamao in Organosilicon and Bioorganosilicon Chemistry (Ed.: ), Ellis Horwood, Chichester, 1985, p. 231.
- 23
- 23aI. Fleming, R. Henning, H. Plaut, J. Chem. Soc. Chem. Commun. 1984, 29;
- 23bI. Fleming, P. E. J. Sanderson, Tetrahedron Lett. 1987, 28, 4229.
- 24For a related example of the migration of a phenyl group from silicon to carbon, see Ref. [23a].
- 25For a review on the cleavage of aryl–silicon bonds, see: C. Eaborn, J. Organomet. Chem. 1975, 100, 43.
- 26This was confirmed by using [D2]-5 a (obtained from [D2]-1 a) for the ring-opening oxidation reaction. See the Supporting Information for details.
