Organic Letters
Letter
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Scheme 4. Thioester Transformation
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a
b
Pd(PPh3)4, CuI, TBAF, and THF; 60 °C; 0.5 h. K2CO3 and DMF;
c
rt; 10 h. PdCl2·dppf, P(2-furyl)3, CuI, Et3N, and DMF; 50 °C; 3 h.
In summary, we have developed a new and efficient Pd-
catalyzed oxidative cross-coupling protocol to construct
thioethers and thioesters that was tuned through ligands on
palladium. A special ligand effect has been uncovered by interval
NMR tracking. Meanwhile, thiosulfate exhibited unique power-
ful advantages of base-free, odorless, and compatibility with
oxidizing reagent. Sole usage of copper salt as both fluoride anion
and oxidant makes the protocol much more practical. Further
application of the ligand control sulfuration and synthetic use are
currently ongoing in our laboratory.
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ASSOCIATED CONTENT
■
S
* Supporting Information
The Supporting Information is available free of charge on the
Procedure, NMR spectra, X-ray data, and analytical data
for all new compounds(PDF)
AUTHOR INFORMATION
■
Corresponding Author
(12) (a) Staunton, J.; Weissman, K. Nat. Prod. Rep. 2001, 18, 380.
(b) Magens, S.; Plietker, B. Chem. - Eur. J. 2011, 17, 8807.
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Manam, R. R.; Mitchell, S. S.; Xu, J.; Teisan, S.; Chao, T.; Deyanat-Yazdi,
G.; Neuteboom, S. T. C.; Lam, K. S.; Potts, B. C. M. J. Nat. Prod. 2007,
Notes
The authors declare no competing financial interest.
́
70, 269. (c) Tulla-Puche, J.; Marcucci, E.; Prats-Alfonso, E.; Bayo-Puxan,
N.; Albericio, F. J. Med. Chem. 2009, 52, 834. (d) Ling, J. J.; Policarpo, R.
L.; Rabideau, A. E.; Liao, X.; Pentelute, B. L. J. Am. Chem. Soc. 2012, 134,
10749.
ACKNOWLEDGMENTS
■
Financial support was provided by NBRPC (973 Program,
2015CB856600), NSFC (21472050, 21272075), NCET
(120178), DFMEC (20130076110023), Fok Ying Tung
Education Foundation (141011), the program for Shanghai
Rising Star (15QA1401800), Professor of Special Appointment
(Eastern Scholar) at Shanghai Institutions of Higher Learning,
and the Changjiang Scholar and Innovative Research Team in
University.
(14) CCDC 1433427: C14H9F3OS, MW = 282.27, monoclinic, space
group P 2(1)/c, final R indices [I > 2σ(I)], R1 = 0.0851, wR2 = 0.2112 R
indices (all data), R1 = 0.1833, wR2 = 0.2840, a = 5.701 (2) Å, b =
14.172 (5) Å, c = 16.101 (6) Å, α = 90°, β = 96.143 (12) deg, γ = 90°, V =
1293.4 (8) Å3, T = 296 (2) K, Z = 4, reflections collected/unique:
14285/2267 (R(int) = 0.1162).
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Sharma, A.; Van der Eycken, E. Adv. Synth. Catal. 2008, 350, 2174.
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948.
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