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Chemical Science
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A. Fedorov, A. A. Toutov, N. A. Swisher and R. H. Grubbs, 24 A. Guijarro and M. Yus, Tetrahedron Lett., 1993, 34, 3487–
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25 C. Däschlein and C. Strohmann, Dalton Trans. 2010, 39,
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26 N-Methylindoles have also been proposed to be
deprotonated in the 2-position by Et3SiH + KOtBu.5
W.-B. Liu, D. P. Schuman, Y.-F. Yang, A. A. Toutov, Y. Liang, H. 27 F. Huber, J. Roesslein and K. Gademann, Org. Lett., 2019, 21,
F. T. Klare, N. Nesnas, M. Oestreich, D. G. Blackmond, S. C.
Virgil, S. Banerjee, R. N. Zare, R. H. Grubbs, K. N. Houk and B.
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S. Banerjee, Y.-F. Yang, I. D. Jenkins, Y. Liang, A. A. Toutov,
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A. A. Toutov, M. Salata, A. Fedorov, Y.-F. Yang, Y. Liang, R.
Cariou, K. N. Betz, E. P. A. Couzijn, J. W. Shabaker, K. N. Houk,
and R. H. Grubbs, Nat. Energy 2017, article number 17008
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A. J. Smith, A. Young, S. Rohrbach, E. F. O’Connor, M. Allison,
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H. Grubbs, US2020/0115396A1, 2020
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28 (a) T. Holm, H. Baumann, H. Lönn, J. Lönngren, H. Nyman and
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29 A. Studer and D. P. Curran, Angew. Chem. Int. Ed., 2011, 50,
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30 An alternative direct fragmentation from 100 103 is also
considered. Vinyl radical fragmentations often have high
energy transition states, but additional driving force is
expected in converting 102 103 as the nitrogen-containing
ring in 102 is not aromatic but becomes aromatic in 103.
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P. Asgari, Y. Hua, C. Thiamsiri, W. Prasitwatcharakorn, A.
Karedath, X. Chen, S. Sardar, K. Yum, G. Leem, B. S. Pierce, K.
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10 A. A. Toutov, K. N. Betz, A. M. Romine and R. H. Grubbs,
US2019/0241587A1, 2019.
11 (a) A. A. Toutov, K. N. Betz, A. M. Romine, R. H. Grubbs, US
2019/0218232A1, 2019. (b) F. Palumbo, S. Rohrbach, T.
Tuttle and J. A. Murphy, Helv. Chim. Acta, 2019, e1900235
12 I. D. Jenkins and E. H. Krenske, ACS Omega, 2020, 5, 7053–
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13 J. N. Arokianathar, K. Kolodziejczak, F. Bugden, K. Clark, T.
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14 A. J. Smith, D. Dimitrova, J. N. Arokianathar, K. Kolodziejczak,
A. Young, M. Alison, D. L. Pole, S. G. Leach, J. A. Parkinson, T.
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15 A. A. Toutov, K. N. Betz, D. P. Schuman, W. B. Liu, A. Fedorov,
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16 S. L. Miller, Science 1953, 117, 528–529.
17 For some previous papers on decyanation, see (a) J. M. R.
Mattalia, Beilstein J. Org. Chem., 2017, 13, 267–284. (b) P. C.
Too, G. H. Chan, Y. L. Tnay, H. Hirao and S. Chiba, Angew.
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18 A. Kaga, H. Hayashi, H. Hakamata, M. Oi, M. Uchiyama, R.
Takita and S. Chiba, Angew. Chem. Int. Ed., 2017, 56, 11807–
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19 (a) E. E. Kwan, Y. Zeng, H. A. Besser and E. N. Jacobsen, Nat.
Chem. 2018, 10, 917–923. (b) A. J. Lennox, Angew. Chem. Int.
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Angew. Chem. Int. Ed., 2019, 58, 16368-16388.
20 We verified that such benzylic nitrile substrates can be
o
o
cyclised also with LiAlH4 at 130 C, although not at 70 C,
again indicative of cyclisation of an iminyl anion – See SI.
21 J. A. Murphy, J. Org. Chem., 2014, 79, 3731–3746.
22 S. S. Hanson, E. Doni, K.T. Traboulsee, G. Coulthard, J. A.
Murphy, and C. A. Dyker, Angew. Chem. Int. Ed., 2015, 54,
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23 R. A. Aitken, A. D. Harper, A. M. Z. Slawin, Synlett, 2017, 28,
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