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ChemComm
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COMMUNICATION
Journal Name
Ogilby. Photocem. Photobiol., 2011, 87: 671–679; H. Li, Y.
Shen, D. Chen, L. Lin, B.C. Wilson, B. Li, S. Xie, J. Fluoresc.,
2013, 23, 41–47.
16 The solubility of 1 and the sensitizer (tetraphenylporphyrin;
DOI: 10.1039/C7CC06214A
17 Regardless of how much
3 is formed, it remains non–
5
6
S. Malashikhin, N.S. Finney, J. Am. Chem. Soc. 2008, 130
,
emissive, and thus invisible to fluorescence visualization.
18 a. J.E. Baldwin, Chem. Soc. Chem. Commun., 1976, 734–736;
J.E. Baldwin, J.A. Reiss, Chem. Soc. Chem. Commun., 1977,
77–77; J.E. Baldwin, R.C. Thomas, L.I. Kruse, L. Silberman, J.
Org. Chem., 1977, 42, 3846–3852; P. Beak, Acc. Chem. Res.,
1992, 25, 215–222, I.V. Alabugin, K. Gilmore, Chem.
12846-12847; R.S. Kathayat, N.S. Finney, J. Am. Chem. Soc.,
2013, 135, 12612-12614; M. Vonlanthen, N.S. Finney, J. Org.
Chem., 2013, 78, 3980-3988; M. Vonlanthen, C.M. Connelly,
A. Deiters, A. Linden, N.S. Finney, J. Org. Chem., 2014, 79
,
6054-6060; R.S. Kathayat, L. Yang, T. Sattasathuchana, L.
Zoppi, K.K. Baldridge, A. Linden, N.S. Finney, J. Am. Chem.
Soc., 2016, 138, 15889-15895.
Commun., 2013, 49, 11246–11250. Note that Baldwin’s rules
relax for third-row elements, such as sulfur. See preceding.
Representative fluorescent probe reviews: J.F. Callan, A.P. De 19 C.S Foote, J.W. Peters., J. Am. Chem. Soc., 1971, 93, 3796–
Silva, D.C. Magri, Tetrahedron, 2005, 61, 8551-8588; A.V.
Tsukanov, A.D. Dubonosov, V.A. Bren, V.I. Minkin. Chem.
Heterocycl. Comp. 2008, 44, 899-923; D.G. Cho, J.L. Sessler,
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Giorgi, M. Micheloni, Coord. Chem. Rev., 2012, 256, 170-192;
X. Li, X. Gao, W. Shi, H. Ma, Chem. Rev., 2013, 114, 590-659;
A. P. Demchenko. Introduction to Fluorescence Sensing.
Second Edition. New York: Springer International Publishing;
2015.
3796; C. S. Foote, J. W. Peters. Int. Congr. Pure Appl. Chem.,
1971, , 129–154. It must be noted that the bis-sulfoxide
forms only in dry, aprotic solvents (benzene, acetonitrile). In
protic solvents, no bis-sulfoxide is formed, only the
monosulfoxide arising from intermolecular reaction. In
contrast, observe that increased % CH3OH increases the
4
proportion of intramolecular reaction of
explain the discrepancy at this time.
1. We are unable to
20 While the boat conformation of 1,4-dithiane is higher in
energy than the chair form, the energetics differ surprisingly
little from those of cyclohexane. Thus, rapid chair-to-chair
inversion at RT, via the requisite boat conformers, is
expected. The conformational energy profile of the cis-bis-
sulfoxide is not unambiguously resolved. See: F.
7
Representative reviews of 1O2 chemistry: a. D.R. Kearns,
Chem. Rev., 1971, 71, 395-427; A. Albini, S.M. Bonesi J.
Photosci., 2003, 10, 1-8; C. Schweitzer, R. Schmidt, Chem.
Rev., 2003, 103, 1685-1757; A. Greer, Accounts Chem. Res.,
2006, 39, 797-804; E.L. Clennan, A. Pace, Tetrahedron, 2005,
61, 6665-6691; P.R. Ogilby. Chem. Soc. Rev. 2010, 39, 3181-
3209.
Lautenschlaeger, G. F. Wright, Can. J. Chem. 1963, 41, 1972-
1983; A. Watanu, Sulfur Reports, 1981, 1, 147-207; F.
8
9
Y. Watanabe, N. Kuriki, K. Ishiguro, Y. Sawaki. J. Am. Chem.
Soc., 1991, 113, 2677-2682; F. Jensen, A. Greer, E.L. Clennan,
J. Am. Chem. Soc., 1998, 120, 4439-4449; E.L. Clennan, Acc.
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Tetrahedron, 2000, 56, 9151-9179.
Freeman, E. Derek, J. Comp. Chem. 2002, 24, 909-919; J. S.
Cruz-Sánchez, E. Juariti, Tetrahedron Lett. 2002, 43, 9369-
9372. Overall, we anticipate the ready availability of
appropriate conformations in seeming sterically congested,
constrained systems, e.g., derivatives of the cis or trans
isomers of 1,2-cyclohexanedithiol.
1
Diphenylsulfoxide (Ph2SO) does not react directly with O2.
However, in the presence of 1O2 and diethylsulfide (Et2S), it is
readily oxidized to diphenylsulfone, providing clear evidence
that the Et2S-derived persulfoxide can oxidize sulfoxides. See
refs 7, 8.
10 There is a structural analogy between the persulfoxide
intermediate and the persulfurate anion (in the form of
Oxone), which is a convenient reagent for the oxidation of
sulfides to sulfoxides and/or sulfones. For example, see: B.
Yu, A.H. Liu, L.N. He, B. Li, Z.F., L.N. Green Chem., 2012, 14
957–962.
,
1
11 For representative discussions of endogenous O2 formed by
non-photochemical methods, see: M. Tarr, D. P. Valenzeno.
Photochem. Photobiol. Sci., 2003, 2, 355–361; M. Davies.
Biochem. Biophys. Res. Comm., 2003, 305, 761-770; Y.
Nishinika, T. Arai, S. Adachi, A. Takaori-Kondo, K. Yamashita.
Biochem. Biophys. Res. Comm., 2011, 413, 75-79; A. N.
Onyango. Oxid. Med. Cell. Longevity, 2016,
12 C. Flors, M.J. Fryer, J. Waring, B. Reeder, U. Bechtold, P.M.
Mullineaux, S. Nonell, M.T. Wilson, N.R. Baker, J. of Exp. Bot.
2006, 57, 1725–1734; X. Raga, D.S.G. Jimenez-Banzo, X.
Batlori, S. Nonell, Chem. Commun., 2009, 2920–2922; A.
Gollmer, J. Arnbjerg, F.H. Blaikie, B.W. Pedersen, T.
Breitenbach, K. Daasbjerg, M. Glasius, P.R. Ogilby. Photocem.
Photobiol., 2011, 87: 671–679; H. Li, Y. Shen, D. Chen, L. Lin,
B.C. Wilson, B. Li, S. Xie, J. Fluoresc., 2013, 23, 41–47.
13 SOSG is commercially available from ThermoFisher Scientific.
14 See Supporting Information.
15 The addition of even small amounts of CH3OH is known to
stabilize persulfoxides. (See ref. 2, and Supporting
Information.) Still, it is not immediately obvious why CH3OH
so strongly influences the ratio of 2:3. See Supporting
Information, Section 6, for discussion.
4 | J. Name., 2012, 00, 1-3
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