Organic Letters
Letter
(5) Representative methodologies on efficient acylation, see:
(a) Peng, P.; Linseis, M.; Winter, R. F.; Schmidt, R. R. J. Am. Chem.
Soc. 2016, 138, 6002. (b) Vedejs, E.; Diver, S. T. J. Am. Chem. Soc.
1993, 115, 3358. (c) Orita, A.; Tanahashi, G.; Kakuda, A.; Otera, J.
Angew. Chem., Int. Ed. 2000, 39, 2877. (d) Procopiou, P. A.; Baugh, S.
P. D.; Flack, S. S.; Inglis, G. G. A. J. Org. Chem. 1998, 63, 2342.
(e) Ishihara, K.; Kubota, M.; Kurihara, H.; Yamamoto, H. J. Org. Chem.
1996, 61, 4560. (f) Vedejs, E.; Diver, S. T. J. Am. Chem. Soc. 1993, 115,
3358.
(6) For selected reports of diacyl disulfide in prebiotic chemistry, see:
(a) Liu, R.; Orgel, L. E. Nature 1997, 389, 52. (b) Leman, L.; Orgel, L.
E.; Ghadiri, M. R. Science 2004, 306, 283. (c) Bowler, F. R.; Chan, C.
K.W.; Duffy, C. D.; Gerland, B.; Islam, S.; Powner, M. W.; Sutherland,
J. D.; Xu, J. F. Nat. Chem. 2013, 5, 383.
considered as the key active acylation intermediate, which then
reacted with the phenol anion 16 and gave the desired phenyl
benzoate 3. As a final note, the generation of phenol anion 16
was possibly the rate-determining step and played a critical role
in the whole acylation sequence, given the phenol’s superior
reactivity toward the more nucleophilic aliphatic alcohol during
the reaction process. Moreover, the acylation of primary or
secondary aliphatic alcohol ought to share a similar mechanistic
process with that of phenol.
In summary, diacyl disulfide was investigated as another
alternatively general and excellent acylation reagent for
acylating both phenolic and aliphatic alcohols apart from
traditional acylation reagents acyl halide and anhydride. It was
compatible with several synthetically significant functionalities
and greatly expanded our understanding in the realm of
protecting group chemistry. Meanwhile, this protocol offered a
new synthetic platform on site-selective acylation of phenolic
hydroxyl group in the presence of alcoholic one, as well as on
cases of primary aliphatic hydroxyl groups in the presence of
other alcoholic groups. The wide utility and potential of this
strategy would be reflected in terms of its rapid access to
selective protection of the hydroxyl group, pharmaceutical and
agrochemical synthesis, and natural product modification as
well as other synergy with strategic transformations enabled by
synthetically robust diacyl disulfide. Thus, our discovery might
open up new vistas for the implementation of diacyl disulfide in
the repertoire of synthetic chemistry and biology.
(7) For a review of prebiotic chemistry, see: Ruiz-Mirazo, K.; Briones,
C.; de la Escosura, A. Chem. Rev. 2014, 114, 285.
(8) (a) Wang, P.; Li, X. C.; Zhu, J. L.; Chen, J.; Yuan, Y.; Wu, X. Y.;
Danishefsky, S. J. J. Am. Chem. Soc. 2011, 133, 1597. (b) Liu, H. X.;
Zhao, L. Y.; Yuan, Y. F.; Xu, Z. F.; Chen, K.; Qiu, S. X.; Tan, H. B.
ACS Catal. 2016, 6, 1732. (c) Mali, S. M.; Bhaisare, R. D.; Gopi, H. N.
J. Org. Chem. 2013, 78, 5550.
(9) (a) Tajbakhsh, M.; Lakouraj, M. M.; Mahalli, M. S. Monatsh.
Chem. 2008, 139, 1453. (b) Jia, X. S.; Liu, X. T.; Li, Q.; Huang, Q.;
Kong, L. L. J. Chem. Res. 2006, 2006, 547. (c) Wang, J. X.; Cui, W. F.;
Hu, Y. L.; Zhao, K. Synth. Commun. 1995, 25, 889.
(10) Most of the diacyl disulfides can be kept under air conditions for
3 d or stirred under water conditions for 12 h without obvious
hydrolysis.
(11) Steglich, W.; Hofle, G. Angew. Chem., Int. Ed. Engl. 1969, 8, 981.
̈
(12) For a review, see: Hofle, G.; Steglich, W.; Vorbruggen, H.
̈
Angew. Chem., Int. Ed. Engl. 1978, 17, 569.
ASSOCIATED CONTENT
* Supporting Information
(13) (a) Wu, W. T.; Zhang, Z. H.; Liebeskind, L. S. J. Am. Chem. Soc.
2011, 133, 14256. (b) Vandavasi, J. K.; Hu, W. P.; Chen, C. Y.; Wang,
J. J. Tetrahedron 2011, 67, 8895.
(14) The diacyl disulfide could be readily accessed according to ref 8c
with slight modification; the details of their preparation are provided in
■
S
The Supporting Information is available free of charge on the
(15) (a) Park, C. M. B.; Johnson, A.; Duan, J. C.; Park, J. J.; Day, J. J.;
Gang, D.; Qian, W. J.; Xian, M. Org. Lett. 2016, 18, 904. (b) Cha, M.
J.; Song, Y. S.; Han, E. G.; Lee, K. J. J. Heterocycl. Chem. 2008, 45, 235.
(16) Paradisi, M. P.; Zecchini, G. P.; Torrini, I. Tetrahedron Lett.
1986, 27, 5029. (b) Ishihara, K.; Kubota, M.; Kurihara, H.; Yamamoto,
H. J. Org. Chem. 1996, 61, 4560. (c) Miyazawa, T.; Yamamoto, M.;
Danjo, H. Monatsh. Chem. 2013, 144, 1351.
Experimental section, detailed experimental procedures,
and full spectroscopic data for all related compounds
AUTHOR INFORMATION
Corresponding Authors
■
(17) Jessen, H.; Schulz, T.; Balzarini, J.; Meier, C. Angew. Chem., Int.
Ed. 2008, 47, 8719. (b) Nagele, E.; Schelhaas, M.; Kuder, N.;
̈
Notes
Waldmann, H. J. Am. Chem. Soc. 1998, 120, 6889. (c) Shi, T. Y.; Chen,
H.; Jing, L. L.; Liu, X. Y.; Sun, X. L.; Jiang, R. Synth. Commun. 2011,
41, 2594.
The authors declare no competing financial interest.
(18) The slightly lower isolated yields in Scheme 4 were mainly
attributed to traces of diacylated esters (usually less than 10% yield).
(19) (a) Ilankumaran, P.; Verkade, J. G. J. Org. Chem. 1999, 64, 9063.
(b) Procopiou, P. A.; Baugh, S. P. D.; Flack, S. S.; Inglis, G. G. A. J.
Org. Chem. 1998, 63, 2342. (c) Orita, A.; Mitsutome, A.; Otera, J. J.
Org. Chem. 1998, 63, 2420. (d) Ishihara, K.; Kurihara, H.; Yamamoto,
H. J. Org. Chem. 1993, 58, 3791.
ACKNOWLEDGMENTS
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This research was funded by the National Science and
Technology Major Projects of China (2014ZX10005002-
005), the National Natural Science Foundation of China
(No. 81502949), and the Natural Science Foundation of
Guangdong Province (2015A030310482, 2016A030313149).
(20) Valadares, J. R.; Singhal, R. L. Science 1968, 159, 990.
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