10.1002/chem.202000721
Chemistry - A European Journal
COMMUNICATION
and K. Ueda, US Pat. 2011/0251403 A1, Central Glass Company, Ltd.,
2011; (c) W.-Y. Fang, G.-F. Zha and H.-L. Qin, Org. Lett., 2019, 21, 8657-
8661.
effective for this reaction. We have also demonstrated that chiral
secondary sulfides can be accessed in high enantiomeric ratios.
The nucleophile scope complements existing phosphine-free
methods. Notably, all of the reactions are complete in less than
30 minutes and can be run at room temperature under ambient
conditions. These mild reaction conditions facilitate reaction
purification and enable telescoping multiple reactions in a single
pot. Efforts to explore this new methodology in the context of
complex pharmaceuticals are currently underway.
[10] A. Ishii, T. Yamazaki and M. Yasumoto, US Pat. 8,426,645B2, Central
Glass Company, Ltd. 2013.
[11] (a) M. Epifanov, P. J. Foth, F. Gu, C. Barrillon, S. S. Kanani, C. S. Higman,
J. E. Hein and G. M. Sammis, J. Am. Chem. Soc., 2018, 140, 16464–
16468; (b) P. J. Foth, F. Gu, T. G. Bolduc, S. S. Kanani and G. M.
Sammis, Chem. Sci., 2019, 10, 10331-10335.
[12] For a study on the effect of halides alpha to the electrophilic center of
SN2 reactions, see: J. Hine and W. H. Brader Jr, J. Am. Chem. Soc., 1953,
75, 3964–3966.
Acknowledgements
[13] The same base that was successfully employed in amine 1,1-
dihydrofluoroalkylation (ref. 11a).
[14] See the SI for further details on solvent optimization.
[15] See the SI for further details on base optimization.
[16] Sharpless and co-workers proposed that catalytic amount of DBU can
facilitate the nucleophilic attack on the S-F bond in Ar-OSO2F through
the fluoride-proton interaction. See: J. Dong, K. B. Sharpless, L. Kwisnek,
J. S. Oakdale and V. V. Fokin, Angew. Chem., Int. Ed., 2014, 53, 9466–
9470.
This work was supported by the University of British Columbia
(UBC), the Natural Sciences and Engineering Research Council
of Canada (NSERC), the NSERC CREATE Sustainable
Synthesis Program for support for JYM and ME.
Keywords: alkyl fluorosulfate • nucleophilic substitution • sulfuryl
[17] For representative examples of nucleophilic catalysis by DBU, see: (a)
W.-C. Shieh, S. Dell and O. Repič, J. Org. Chem., 2002, 67, 2188–2191;
(b) V. Gembus, F. Marsais and V. Levacher, Synlett., 2008, 1463-1466;
(c) J. E. Taylor, S. D. Bull and J. M. J. Williams, Chem. Soc. Rev., 2012,
41, 2109–2121.
fluoride • amines • alkylation
[1]
[2]
(a) O. Mitsunobu and M. Yamada, Bull. Chem. Soc. Jpn., 1967, 40, 2380;
(b) O. Mitsunobu, M. Yamada and T. Mukaiyama, Bull. Chem. Soc. Jpn.,
1967, 40, 935.
[18] For the reaction of phthalimide with a representative secondary alcohol,
see the SI (page S28).
For representative reviews, see: (a) K. C. Kumara Swamy, N. N. Bhuvan
Kumar, E. Balaraman and K. V. P. Pavan Kumar Chem. Rev., 2009, 109,
2551–265; (b) J. An, R. M. Denton, T. H. Lambert and E. D. Nacsa, Org.
Biomol. Chem., 2014, 12, 2993; (c) S. Fletcher, Org. Chem. Front., 2015,
2, 739-752; (d) R. H. Beddoe, H. F. Sneddon and R. M. Denton, Org.
Biomol, Chem., 2018, 16, 7774-7781; (e) P. H. Huy, Eur. J. Org. Chem.,
10.1002/ejoc.201901495.
[19] Predicted pKa values from SciFinder: HNPhth pKa = 10.39 0.20,
HNBoc2 pKa = 8.25 0.46, and PhSO2NHOMe pKa = 6.24 0.40.
[20] More nucleophilic thiols can competitively react with sulfuryl fluoride, see
ref. 11b for details.
[21] These products can be desulfonylated using numerous literature
methods. For a representative review, see: D. A. Alonso, C. N. Ájera, in
Organic Reactions (Ed.: John Wiley & Sons, Inc.), John Wiley & Sons,
Inc., Hoboken, NJ, USA, 2009, pp. 367–656.
[3]
[4]
See: S. Dandapani and D. P. Curran, Chem. - Eur. J., 2004, 10, 3130–
3138 and references therein.
[22] Purification was achieved using a simple diethyl ether extraction followed
by a hexane wash.
(a) For a representative review, see: R. Dembinski, Eur. J. Org. Chem.,
2004, 2004, 2763–2772; (b) For a recent example of organocatalytic
Mitsunobu using a P(V) reagent, see: R. H. Beddoe, K. G. Andrews, V.
Magné, J. D. Cuthbertson, J. Saska, A. L. Shannon-Little, S. E.
Shanahan, H. F. Sneddon and R. M. Denton, Science, 2019, 365, 910–
914. (c) For an example of preparing alkyl azides with
diphenylphosphoryl azide, see: A. S. Thompson, G. R. Humphrey, A. M.
DeMarco, D. J. Mathre, E. J. J. Grabowski, J. Org. Chem., 1993, 58,
5886–5888.
[23] Both sulfones are commonly used as precursors for Julia olefination: (a)
J. B. Baudin, G. Hareau, S. A. Julia and O. Ruel, Tetrahedron Lett., 1991,
32, 1175–1178; (b) P. R. Blakemore, W. J. Cole, P. J. Kocienski and A.
Morley, Synlett., 1998, 26–28.
[24] 25a can also be efficiently converted to alkyl sulfones and sulfonamides,
see: J. J. Day, D. L. Neill, S. Xu and M. Xian Org. Lett., 2017, 19, 3819–
3822.
[5]
For representative examples, see: (a) A. G. M. Barrett, D. C. Braddock,
R. A. James, N. Koike and P. A. Procopiou, J. Org. Chem., 1998, 63,
6273–6280; (b) Y. Kawano, N. Kaneko and T. Mukaiyama Chem. Lett.,
2005, 34, 1612–1613. For the use of catalytic Vilsmeier reagent, see: (c)
P. H. Huy, S. Motsch, S. M. Kappler, Angew. Chem., Int. Ed., 2016, 55,
1–6; (d) P. H. Huy, I. Filbrich, Chem. Eur. J., 2018, 24, 7410–7416.
E. D. Nacsa and T. H. Lambert, Org. Lett., 2013, 15, 38-41.
(a) A. Bunrit, C. Dahlstrand, S. K. Olsson, P. Srifa, G. Huang, A. Orthaber,
P. J. R. Sjꢀberg, S. Biswas, F. Himo and J. S. M. Samec, J. Am. Chem.
Soc., 2015, 137, 4646–4649; (b) P. T. Marcyk, L. R. Jefferies, D. I.
AbuSalim, M. Pink, M.-H. Baik and S. P. Cook, Angew. Chem., Int. Ed.,
2019, 58, 1727 –1731.
[6]
[7]
[8]
For representative examples, see: (a) J. Dong, L. Krasnova, M. G. Finn
and K. B. Sharpless, Angew. Chem., Int. Ed., 2014, 53, 9430–9448; (b)
P. S. Hanley, M. S. Ober, A. L. Krasovskiy, G. T. Whiteker and W. J.
Kruper, ACS Catal., 2015, 5, 5041–5046; (c) M. K. Nielsen, C. R. Ugaz,
W. Li, A. G. Doyle, J. Am. Chem. Soc., 2015, 137, 9571–9574. (d) S. D.
Schimler, M. A. Cismesia, P. S. Hanley, R. D. J. Froese, M. J. Jansma,
D. C. Bland and M. S. Sanford, J. Am. Chem. Soc., 2017, 139, 1452–
1455; (e) P. R. Melvin, D. M. Ferguson, S. D. Schimler, D. C. Bland and
M. S. Sanford, Org. Lett., 2019, 21, 1350–1353.
[9]
(a) G.-F. Zha, W.-Y. Fang, Y.-G. Li, J. Leng, X. Chen and H.-L. Qin, J.
Am. Chem. Soc., 2018, 140, 17666–17673; (b) A. Ishii, M. Yasumoto
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