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Chemical Science
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ARTICLE
Journal Name
9
For a comprehensive review on DoM reactions, see: (a) J. 24 (a) W. C. Black, B. Guay and F. Scheuermeyer, J. Org. Chem.,
Board, J. L. Cosman, T. Rantanen, S. P. Singh and V. Snieckus,
Platin. Met. Rev., 2013, 57, 234–258. (b) V. Snieckus and T.
Macklin, in Handbook of C–H Transformations: Applications in
Organic Synthesis, ed. G. Dyker, Wiley-VCH Verlag GmbH,
DOI: 10.1039/C9SC06060J
Angew. Chem. Int. Ed., 2007, 46, 7685–7688. (c) T. Bresser, G.
Monzon, M. Mosrin and P. Knochel, Org. Process Res. Dev.,
2010, 14, 1299–1303.
Weinheim, Germany, 2008, vol. 1, pp. 106–115. (c) V. 25 S. P. Shahi and K. Koide, Angew. Chem. Int. Ed., 2004, 43,
Snieckus, Chem. Rev., 1990, 90, 879–933; (d) P. Beak and V. 2525–2527.
Snieckus, Acc. Chem. Res., 1982, 15, 306–312. For stereo- and 26 K. Murakami, K. Hirano, H. Yorimitsu and K. Oshima, Angew.
regiocontrolled deprotonative metalation of various types of Chem. Int. Ed., 2008, 47, 5833–5835.
C–H bonds by utilizing complex-induced proximity effects, 27 W. Nakanishi, M. Yamanaka and E. Nakamura, J. Am. Chem.
see: (e) P. Beak and A. I. Meyers, Acc. Chem. Res., 1986, 19,
Soc., 2005, 127, 1446–1453.
356–363.
28 (a) G. De Martino, G. La Regina, A. Coluccia, M. C. Edler, M. C.
Barbera, A. Brancale, E. Wilcox, E. Hamel, M. Artico and R.
Silvestri, J. Med. Chem., 2004, 47, 6120–6123; (b) G. Liu, J. R.
Huth, E. T. Olejniczak, R. Mendoza, P. DeVries, S. Leitza, E. B.
Reilly, G. F. Okasinski, S. W. Fesik and T. W. von Geldern, J.
Med. Chem., 2001, 44, 1202–1210; (c) A. Marcincal-Lefebvre,
J. C. Gesquiere, C. Lemer and B. Dupuis, J. Med. Chem., 1981,
24, 889–893.
10 For a review on deprotonative metalation using metal amide
bases, see: (a) F. Chevallier, F. Mongin, R. Takita and M.
Uchiyama, in Arene Chemistry, ed. J. Mortier, John Wiley &
Sons, Inc, Hoboken, New Jersey, 2015, pp 777–812; (b) R. E.
Mulvey, F. Mongin, M. Uchiyama and Y. Kondo, Angew. Chem.
Int. Ed., 2007, 46, 3802–3824.
11 Cyanide anion should play an important roll in the
deprotonation step rather than the iodination step (Scheme 29 Several diaryl disulfide syntheses via the reaction of diaryl
S1).
disulfide and either aryl lithium or aryl Grignard reagents have
been reported, see: Li: (a) G. D. Figuly and J. C. Martin, J. Org.
Chem., 1980, 45, 3728–3729; (b) J. M. Muchowski and M. C.
Venuti, J. Org. Chem., 1980, 45, 4798–4801. Mg: (c) B.-X. Du,
Z.-J. Quan, Y.-X. Da, Z. Zhang and X.-C. Wang, Adv. Synth.
Catal., 2015, 357, 1270–1276.
12 CuCN 0.84 USD/mmol (47.00 USD/5 g) vs AgCN 0.85
USD/mmol (63.80 USD/10 g) at Sigma-Aldrich, Nov. 27th 2019.
i
13 Hydride elimination from Pr2N anion might account for the
low reactivity of the corresponding amidoargentate, see: B.-
A. Feit, S. Shapira and A. Herbst, Tetrahedron, 1995, 51, 317–
328.
30 Knochel et al. recently reported diaryl sulfide synthesis
utilizing aromatic zinc reagents, see; Z.-B. Dong, M.
Balkenhohl, E. Tan and P. Knochel, Org. Lett., 2018, 20, 7581–
7584.
14 Cy2NH (0.051 USD/mmol; 27.90 USD/100 g) is less expensive
than TMPH (0.72 USD/mmol; 128.00 USD/25 g) at Sigma-
Aldrich, Nov. 27th 2019. Knochel discussed this issue: (a) M. R.
Becker and P. Knochel, Org. Lett., 2016, 18, 1462–1465; (b) M. 31 H. A. Stefani, J. M. Pena, F. Manarin, R. A. Ando, D. M. Leal and
R. Becker, M. A. Ganiek and P. Knochel, Chem. Sci., 2015, 6,
6649–6653.
15 S. Usui, Y. Hashimoto, J. V. Morey, A. E. H. Wheatley and M.
Uchiyama, J. Am. Chem. Soc., 2007, 129, 15102–15103.
16 The inability to metalate 1a in dioxane might be attributed to
undesired reaction of the putative argentate with dioxane.
N. Petragnani, Tetrahedron Lett., 2011, 52, 4398–4401.
32 Diazo Chemistry I, ed. H. Zollinger, VCH Verlagsgesellschaft
mbH, Weinheim, 1994.
33 (a) Y. Takeda, S. Okumura and S. Minakata, Synthesis, 2013,
45, 1029–1033. (b) Y. Takeda, S. Okumura and S. Minakata,
Angew. Chem. Int. Ed., 2012, 51, 7804–7808.
For related work, see: J. García-Álvarez, E. Hevia, A. R. 34 N. Tezuka, K. Shimojo, K. Hirano, S. Komagawa, K. Yoshida, C.
Kennedy, J. Klett and R. E. Mulvey, Chem. Commun., 2007,
2402–2404.
Wang, K. Miyamoto, T. Saito, R. Takita and M. Uchiyama, J.
Am. Chem. Soc., 2016, 138, 9166–9171.
17 THF was included while the crude 3 was processed with THF.
For details, see ESI.
18 A. J. Peel, N. Tezuka, J. M. D’Rozario, M. Uchiyama and A. E. H.
Wheatley, Chem. Sci., 2019, 10, 3385–3400.
19 The excellent compatibility of DoAg with nucleophile-
sensitive AFGs such as ethyl and methyl esters and aldehyde
(Table 2, 2g, 2h and 2u) rules out the formation of arylllithium.
For the condensation of ortho-lithiated benzoates, see: (a) T.
D. Krizan and J. C. Martin, J. Am. Chem. Soc., 1983, 105, 6155–
6157. (b) C. J. Upton and P. Beak, J. Org. Chem., 1975, 40,
1094–1098. (c) W. E. Parham and Y. A. Sayed, J. Org. Chem.,
1974, 39, 2053–2056.
20 J. A. Garden, D. R. Armstrong, W. Clegg, J. García-Alvarez, E.
Hevia, A. R. Kennedy, R. E. Mulvey, S D. Robertson and L.
Russo, Organometallics, 2013, 32, 5481–5490.
21 SF5 (super trifluoromethyl) is an attractive functional group.
Its chemical and physical properties are receiving increasing
attention in the pharmaceutical sciences, see: Fluorine in
Pharmaceutical and Medicinal Chemistry; Molecular Medicine
and Medicinal Chemistry, ed. V. Gouverneur and K. Müller,
Imperial College Press, Covent Garden, London, 2012.
22 NBO analysis by modeled DFT calculation estimates that the
lithium argentate derived from PhSF5 has a strong interaction
between Li and F (10.2 kcal/mol), while PhCF3 has a moderate
Li–F interaction (6.1 kcal/mol) (see ESI).
23 (a) G. Bartoli, R. Dalpozzo and M. Nardi, Chem. Soc. Rev., 2014,
43, 4728–4750. (b) M. Mąkosza, Chem. Eur. J., 2014, 20, 5536–
5545.
6 | J. Name., 2012, 00, 1-3
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