Organic Letters
Letter
1
Experiment details, spectral data, copies of H and 13C
(20) Chloro sulfide 6 was prepared independently by addition of
PhSCl to chalcone. See the SI for more details.
(21) We propose that the additional PhICl2 equivalent rapidly
oxidizes the in situ generated PhSCl to PhSCl3 which undergoes
stereoselective anti-addition to chalcone. The resulting anti-β-
chlorophenylsulfonium dichloride intermediate collapses stereospecifi-
cally to anti-dichloride 7. For similar reactivity of PhSeCl3 with
alkenes, see: (a) Garratt, D. G.; Schmid, G. H. Can. J. Chem. 1974, 52,
3599. (b) Engman, L. J. Org. Chem. 1987, 52, 4086.
(22) Colins, C. C.; Cronin, M. F.; Moynihan, H. A.; McCarthy, D. G.
J. Chem. Soc., Perkin Trans. 1 1997, 1267.
(23) For reproducibility issues arising from the quality of PhICl2, see
for example: Nicolaou, K. C.; Simmons, N. L.; Ying, Y.; Heretsch, P.
M.; Chen, J. S. J. Am. Chem. Soc. 2011, 133, 8134.
(24) Zhao, X.-F.; Zhang, C. Synthesis 2007, 2007, 551.
(25) (a) Using PhI/NaOCl/HCl in ref 24. (b) Baranowski, A.;
Plachta, D.; Skulski, L.; Klimaszewska, M. J. Chem. Res. 2000, 435.
(26) Murphy, M.; Lynch, D.; Schaeffer, M.; Kissane, M.; Chopra, J.;
O’Brien, E.; Ford, A.; Ferguson, G.; Maguire, A. R. Org. Biomol. Chem.
2007, 5, 1228.
X-ray crystallographic data for (R)-4l (CIF)
X-ray crystallographic data for syn-chloro sulfide 6b
AUTHOR INFORMATION
Corresponding Authors
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ORCID
Author Contributions
†D.C. and S.L. contributed equally.
Notes
(27) Tuleen, D. L.; Stephens, T. B. J. Org. Chem. 1969, 34, 31.
(28) In addition to anti-chloro sulfide 6, regioisomeric anti-chloro
sulfide 6a was also formed. For characterization of 6a and synthesis of
syn-chloro sulfide 6b, see the SI.
(29) Taniguchi, T.; Fujii, T.; Ishibashi, H. J. Org. Chem. 2010, 75,
8126.
(30) Chauhan, P.; Mahajan, S.; Enders, D. Chem. Rev. 2014, 114,
8807.
(31) Fang, X.; Li, J.; Wang, C.-J. Org. Lett. 2013, 15, 3448.
(32) (a) Ray, D. G., III; Koser, G. F. J. Am. Chem. Soc. 1990, 112,
5672. (b) Koser, G. F.; Kokil, P. B.; Shah, M. Tetrahedron Lett. 1987,
28, 5431.
(33) (a) Liu, Z.-D.; Chen, Z.-C. Heteroat. Chem. 1992, 3, 559.
(b) Combes, S.; Finet, J.-P. Tetrahedron 1998, 54, 4313. (c) Kang, S.-
K.; Ryu, H.-C.; Lee, S.-W. J. Organomet. Chem. 2000, 610, 38.
(d) Burford, N.; Clyburne, J. A. C.; Gates, D. P.; Schriver, M. J.;
Richardson, J. F. J. J. Chem. Soc., Dalton Trans. 1994, 997.
(34) Zhdankin, V. V. Hypervalent Iodine Chemistry; Wiley: Chichester,
2014.
(35) Ochiai, M.; Sueda, T.; Miyamoto, K.; Kiprof, P.; Zhdankin, V. V.
Angew. Chem., Int. Ed. 2006, 45, 8203.
(36) For oxidative dichlorination of metal complexes with PhICl2, see
for example: (a) Whitfield, S. R.; Sanford, M. S. J. Am. Chem. Soc.
2007, 129, 15142. (b) McCall, A. S.; Wang, H.; Desper, J. M.; Kraft, S.
J. Am. Chem. Soc. 2011, 133, 1832.
(37) Cartwright, M.; Woolf, A. A. J. Fluorine Chem. 1981, 19, 101.
(38) (a) Tanioku, A.; Nakai, T.; Hayashi, S.; Nakanishi, W. Heteroat.
Chem. 2011, 22, 446. (b) Baenziger, N. C.; Buckles, R. E.; Maner, R. J.;
Simpson, T. D. J. Am. Chem. Soc. 1969, 91, 5749. (c) Wilson, G. E., Jr.;
Chang, M. M. Y. J. Am. Chem. Soc. 1974, 96, 7533.
(39) For a ReactNMR observation of a diastereomeric chlorosulfo-
nium salt generated with NCS, see: Foley, D. A.; Doecke, C. W.;
Buser, J. Y.; Merritt, J. M.; Murphy, L.; Kissane, M.; Collins, S. G.;
Maguire, A. R.; Kaerner, A. J. Org. Chem. 2011, 76, 9630.
(40) Brucks, A. P.; Treitler, S.-A.; Liu, D. S.; Snyder, S. A. Synthesis
2013, 45, 1886.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was supported by Enterprise-Ireland CF Fund
(CF20144034), H2020-RISE (OCN4OS), and IRC (GOIPG/
2015/3942). We thank Dr. Brendan Twamley (TCD) for X-ray
analysis.
REFERENCES
■
(1) For a key review, see: Chung, W.-J.; Vanderwal, C. D. Angew.
Chem., Int. Ed. 2016, 55, 4396.
(2) Bohlmann, R. In Comprehensive Organic Transformations, 2nd ed.;
Larock, R. C., Ed.; Wiley-VCH: New York, 1999; pp 689−702.
(3) For example, see: (a) Cahiez, G.; Lefevre, N.; Poizat, M.;
̀
Moyeux, A. Synthesis 2013, 45, 231. (b) Liu, Y.; Xu, Y.; Jung, S. H.;
Chae, J. Synlett 2012, 23, 2692. (c) Braddock, D. C.; Pouwer, R. H.;
Burton, J. W.; Broadwith, P. J. Org. Chem. 2009, 74, 6042.
(4) Recent examples: (a) Moerdyk, J. P.; Bielawski, C. W. Chem. -
Eur. J. 2014, 20, 13487. (b) Nguyen, T. V.; Bekensir, A. Org. Lett.
2014, 16, 1720. (c) Villalpando, A.; Ayala, C. E.; Watson, C. B.;
Kartika, R. J. Org. Chem. 2013, 78, 3989.
(5) (a) Appel, R. Angew. Chem., Int. Ed. Engl. 1975, 14, 801.
(b) Pluempanupat, W.; Chantarasriwong, O.; Taboonpong, P.; Jang,
D. O.; Chavasiri, W. Tetrahedron Lett. 2007, 48, 223.
(6) For thia-Apple type chlorination of alkyl thiols, see: (a) Weiss, R.
G.; Snyder, E. J. Chem. Commun. 1968, 1358. (b) Still, I. W. J.; Kutney,
G. W.; McLean, D. J. Org. Chem. 1982, 47, 560.
(7) Denton, R. M.; An, J.; Adeniran, B. Chem. Commun. 2010, 46,
3025.
(8) An, J.; Denton, S. M.; Lambert, T. H.; Nacsa, E. D. Org. Biomol.
Chem. 2014, 12, 2993.
(9) Hugenberg, V.; Haufe, G. J. Fluorine Chem. 2012, 143, 238.
(10) Sugiyama, S.; Diakur, J. M. Org. Lett. 2000, 2, 2713.
(11) Ichikawa, J.; Sugimoto, K.; Sonoda, T.; Kobayashi, H. Chem.
Lett. 1987, 16, 1985.
(12) York, C.; Prakash, G. K. S.; Olah, G. A. Tetrahedron 1996, 52, 9.
(13) For SN2 chlorination of a benzylic arylsulfoxide, see: Pinna, G.;
Bellucci, M. C.; Malpezzi, L.; Pisani, L.; Superchi, S.; Volonterio, A.;
Zanda, M. Tetrahedron 2011, 67, 5268.
(14) Stewart, J. M.; Cordts, H. P. J. Am. Chem. Soc. 1952, 74, 5880.
(15) Bordwell, F. G.; Pitt, B. M. J. Am. Chem. Soc. 1955, 77, 572.
(16) Schreiber, K. C.; Fernandez, V. P. J. Org. Chem. 1961, 26, 2910.
(17) Dilworth, B. M.; McKervey, M. A. Tetrahedron 1986, 42, 3731.
(18) (a) Shi, L.; Horn, M.; Kobayashi, S.; Mayr, H. Chem. - Eur. J.
2009, 15, 8533. (b) Orlovic,
1983, 48, 2278.
́ ̌ ́
M.; Polla, E.; Borcic, S. J. Org. Chem.
(19) Le Roux, C.; Gaspard-Iloughmane, H.; Dubac, J. J. Org. Chem.
1994, 59, 2238.
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