Journal of the American Chemical Society
Page 6 of 7
Schulz, E. Chem. Rev. 2007, 107, 513. For recent examples,
sented. This is the first general example of alkyl sulfenate
anions employed in transition metal catalysis. The alkyl sulꢀ
fenate anions were generated in situ by a fluoride triggered
elimination strategy from 2ꢀ(trimethylsilyl)ethyl alkyl sulfoxꢀ
ides under weakly basic conditions. The key to success of this
method is avoidance of strong bases and high temperature
see: d) Stang, E. M.; White, M. C. J. Am. Chem. Soc. 2011, 133,
14892; e) Dornan, P. K.; Leung, P. L.; Dong, V. M. Tetrahe-
dron 2011, 67, 4378; f) Chen. J.; Chen, J.; Lang, F.; Zhang, X.;
Cun, L.; Zhu, J.; Deng, J.; Liao, J. J. Am. Chem. Soc. 2010, 132,
4552 g) Trost, B. M.; Ryan, M. C.; Rao, M.; Markovic, T. Z. J.
Am. Chem. Soc. 2014, 136, 17422.
a) Wojaczyńska, E.; Wojaczyński, J. Chem. Rev. 2010, 110,
4303; b) O’Mahony, G. E.; Kelly, P.; Lawrence, S. E.; Maguire,
A. R. Arkivoc 2011, 1, 1; c) Bolm, C. Coord. Chem. Rev. 2003,
237, 245.
For reviews, see: a) O'Donnell, J. S.; Schwan, A. L. J. Sulfur.
Chem. 2004, 25, 183; b) Maitro, G.; Prestat, G.; Madec, D.;
Poli, G. Tetrahedron: Asymmetry 2010, 21, 1075; c) Schwan, A.
L.; Söderman, S. C. Phosphorus, Sulfur Silicon, Relat. Elem.
2013, 188, 275; for sulfenate anions as catalyst, see: d) Zhang,
M.; Jia, T.; Yin, H.; Carroll, P. J.; Schelter, E. J.; Walsh, P. J.
Angew. Chem., Int. Ed. 2014, 53, 10755; e) Zhang, M.; Jia, T.;
Wang, C. Y.; Walsh, P. J. J. Am. Chem. Soc. 2015, 137,10346;
for sulfenate anions in enantioselective alkylation, see: f) Zhong,
L.; Ban, X.; Kee, C. W.; Tan, C.ꢀH. Angew. Chem,. Int. Ed.
2014, 53, 11849.
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(>100 C), as well as the utilization of highly selective cataꢀ
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lysts for the arylation of alkyl sulfenate anions. Given the
wide variety of aryl bromides or chlorides commercially availꢀ
able, this method enables the synthesis of a vast array of funcꢀ
tionalized alkyl aryl sulfoxides. We anticipate that this apꢀ
proach will be adopted to prepare diverse aryl alkyl sulfoxides
for use in medicinal chemistry.
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ASSOCIATED CONTENT
Supporting Information. Procedures and full characterizaꢀ
tion of new compounds. This material is available free of charge
10 a) Maitro, G.; Vogel, S.; Prestat, G.; Madec, D.; Poli, G. Org.
Lett. 2006, 8, 5951; b) Maitro, G.; Vogel, S.; Sadaoui, M.;
Prestat, G.; Madec, D.; Poli, G. Org. Lett. 2007, 9, 5493.
AUTHOR INFORMATION
Corresponding Author
11
Bernoud, E.; Le Duc, G.; Bantreil, X.; Prestat, G.; Madec, D.;
Poli, G. Org. Lett. 2010, 12, 320.
*pwalsh@sas.upenn.edu
Notes
The authors declare no competing financial interests.
12 Izquierdo, F.; Chartoire, A.; Nolan, S. P. ACS Cat. 2013, 3, 2190.
13 a) Jia, T.; Bellomo, A.; Montel, S.; Zhang, M.; El Baina, K.; Zheng,
B.; Walsh, P. J. Angew. Chem., Int. Ed. 2014, 53, 260; b) Jia, T.;
Zhang, M.; Sagamanova, I. K.; Wang, C. Y.; Walsh, P. J. Org.
Lett. 2015, 17, 1168.
14 a) Gelat, F.; Lohier, J.ꢀF.; Gaumont, A.ꢀC.; Perrio, S. Adv. Synth.
Catal. 2015, 357, 2011. Notably, only methyl and benzyl sulꢀ
foxides were reported in poor to modest yields (19%, 40%) for
long reaction times (up to 5 days). tertꢀButyl sulfoxides have
been firstly utilized as precursors to generate aryl sulfenate aniꢀ
ons under basic conditions by Walsh group, see: b) Zhang, M.;
Jia, T.; Sagamanova, I. K.; Pericas, M. A.; Walsh, P. J. Org.
Lett. 2015, 17, 1164.
15 There was a single substrate of alkyl sulfenate anion with beta
protons in palladium catalysis, see: reference 13a; there were
two examples of benzyl sulfenate anions in cross coupling reacꢀ
tions, see reference 10b.
16 Foucoin, F.; Caupène, C.; Lohier, J.ꢀF.; de Oliveira Santos, J. S.;
Perrio, S.; Metznera, P. Synthesis 2007, 1315.
ACKNOWLEDGMENT
We thank National Science Foundation [CHEꢀ1152488] for finanꢀ
cial support. H.J. thanks China Scholarship Council
[20140635137] for financial support.
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