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X
SH
S
Mn* (1.0 equiv)
THF/rt/0.5 h
ArCOCl (2.0 equiv)
THF/rt/0.5 h
O
no additive
(2.0 equiv)
X = H (6a, 96%)
X = 3-Br (6b, 85%)
X = 4-F (6c, 80%)
Scheme 3 Acylations of benzenethiol
To demonstrate the practicality and robustness of this
method, we applied our approach to the reaction with
2,4,6-trichloro-1,3,5-triazine (TCT), an efficient reagent for
further transformations in organic synthesis. Under the
conditions shown in Scheme 4, the whole procedure pro-
ceeded smoothly to give product 7 exclusively in 53% isolat-
ed yield, even at an elevated temperature and with an ex-
tended reaction time.
Cl
N
N
Cl
N
O
O
Cl
N
Cl
OH
N
N
Mn* (2.0 equiv)
THF/rt/10 min
1.0 equiv
THF/reflux/6.0 h
no additive
(4.0 equiv)
7 (53%)
Scheme 4 Reaction with TCT
In conclusion, we have demonstrated another applica-
tion of highly active manganese (Mn*) in organic synthesis:
catalyst-free Mn*-mediated O- and S-acylations of alcohols
and thiols, respectively, with acid chlorides or acetic anhy-
dride under mild conditions.10 In addition, it should be not-
ed that, unlike a previous method,3 our method uses an en-
vironmentally friendly metal (Mn*) and has an easy work-
up procedure. Although the exact role of the highly active
manganese is unclear at this time, this approach can pro-
vide an alternative and simple route to O-acylation of alco-
hols or S-acylation of thiols. Further studies to elucidate the
reactivity of highly active manganese are currently under-
way in our laboratory.
(4) Unpublished results from our laboratory; Zn* (1.0 equiv)
reacted with 3- or 4-iodophenol (1.0 equiv), and the resulting
complex was coupled with acid chlorides to give the corre-
sponding phenyl benzoate esters instead of the expected
Negishi ketone products.
(5) Durán-Peña, M. J.; Botubol-Ares, J. M.; Hanson, J. R.; Hernández-
Galán, R.; Collado, I. G. Eur. J. Org. Chem. 2016, 3584.
Acknowledgment
(6) Kim, S.-H.; Rieke, R. D. Tetrahedron Lett. 1999, 40, 4931.
(7) (a) Shinntou, T.; Fukumoto, K.; Mukaiyama, T. Bull. Chem. Soc.
Jpn. 2004, 77, 1569. (b) Lee, C. K.; Yu, J. S.; Lee, H.-J. J. Heterocycl.
Chem. 2002, 39, 1207.
This research was financially supported by a fund from Dankook Uni-
versity in 2016.
(8) (a) Kamm, O.; Kamm, W. F. Org. Synth. Coll. Vol. I; Wiley:
London, 1941, 2nd ed. 104. (b) Ong, G. S. Y.; Somerville, C. P.;
Jones, T. W.; Walsh, J. P. Case Rep. Med. 2012, 384054, DOI:
10.1155/2012/384054.
(9) (a) Phukan, P. Tetrahedron Lett. 2004, 45, 4785. (b) Larock, R. C.
Comprehensive Organic Transformations: A Guide to Functional
Group Preparations; VCH: New York, 1989, 980.
(10) Phenyl 3-Chlorobenzoate (1c); Typical Procedure
A 25 mL flask was charged with lithium (0.07 g, 9.68 mmol),
naphthalene (0.19 g, 1.48 mmol), anhyd MnI2 (1.45 g,
References and Notes
(1) Green’s Protective Groups in Organic Synthesis; Wuts, P. G. M.;
Greene, T. W., Eds.; Wiley-Interscience: Hoboken, 2007, 4th ed.
(2) For recent reports, see: (a) Prajapti, S. K.; Nagarsenkar, A.; Babu,
B. N. Tetrahedron Lett. 2014, 55, 910. (b) Liu, Z.; Ma, Q.; Liu, Y.;
Wang, Q. Org. Lett. 2014, 16, 236. (c) Lu, N.; Chang, W.-H.; Tu,
W.-H.; Li, C.-K. Chem. Commun. 2011, 47, 727. (d) Vuluga, D.;
Legros, J.; Crousse, B.; Bonnet-Delpon, D. Chem. Eur. J. 2010, 16,
© Georg Thieme Verlag Stuttgart · New York — Synlett 2017, 28, A–E