Organic Letters
Letter
(8) (a) Migita, T.; Shimizu, T.; Asami, Y.; Shiobara, J.-i.; Kato, Y.;
Kosugi, M. The Palladium Catalyzed Nucleophilic Substitution of
Aryl Halides by Thiolate Anions. Bull. Chem. Soc. Jpn. 1980, 53,
thiolation of terminal olefins and alkynes. Tetrahedron Lett. 2015, 56,
6022−6029.
(14) Tamai, T.; Ogawa, A. Regioselective Hydrothiolation of
Alkenes Bearing Heteroatoms with Thiols Catalyzed by Palladium
Diacetate. J. Org. Chem. 2014, 79, 5028−5035.
́
1385−1389. (b) Fernandez-Rodríguez, M. A.; Shen, Q.; Hartwig, J. F.
A General and Long-Lived Catalyst for the Palladium-Catalyzed
Coupling of Aryl Halides with Thiols. J. Am. Chem. Soc. 2006, 128,
2180−2181. (c) Oderinde, M. S.; Frenette, M.; Robbins, D. W.;
Aquila, B.; Johannes, J. W. Photoredox Mediated Nickel Catalyzed
Cross-Coupling of Thiols With Aryl and Heteroaryl Iodides via Thiyl
Radicals. J. Am. Chem. Soc. 2016, 138, 1760−1763. (d) Ichiishi, N.;
(15) DuBois, M. R. Catalytic applications of transition-metal
complexes with sulfide ligands. Chem. Rev. 1989, 89, 1−9.
(16) (a) Jimenez Rodriguez, C.; Foster, D. F.; Eastham, G. R.; Cole-
Hamilton, D. J. Highly selective formation of linear esters from
terminal and internal alkenes catalysed by palladium complexes of bis-
(di-tert-butylphosphinomethyl)benzene. Chem. Commun. 2004,
́
Malapit, C. A.; Wozniak, Ł.; Sanford, M. S. Palladium- and Nickel-
1720−1721. (b) Roesle, P.; Durr, C. J.; Moller, H. M.; Cavallo, L.;
̈
̈
Catalyzed Decarbonylative C−S Coupling to Convert Thioesters to
Thioethers. Org. Lett. 2018, 20, 44−47. (e) Jones, K. D.; Power, D. J.;
Bierer, D.; Gericke, K. M.; Stewart, S. G. Nickel Phosphite/
Phosphine-Catalyzed C−S Cross-Coupling of Aryl Chlorides and
Thiols. Org. Lett. 2018, 20, 208−211. (f) Liu, C.; Szostak, M.
Decarbonylative thioetherification by nickel catalysis using air- and
moisture-stable nickel precatalysts. Chem. Commun. 2018, 54, 2130−
Caporaso, L.; Mecking, S. Mechanistic Features of Isomerizing
Alkoxycarbonylation of Methyl Oleate. J. Am. Chem. Soc. 2012, 134,
17696−17703.
(17) (a) Harrod, J. F.; Chalk, A. J. Homogeneous Catalysis. I.
Double Bond Migration in n-Olefins, Catalyzed by Group VIII Metal
Complexes. J. Am. Chem. Soc. 1964, 86, 1776−1779. (b) Sparke, M.
B.; Turner, L.; Wenham, A. J. M. The isomerization of olefins by
palladium complexes. J. Catal. 1965, 4, 332−340. (c) Tan, E. H. P.;
Lloyd-Jones, G. C.; Harvey, J. N.; Lennox, A. J. J.; Mills, B. M.
[(RCN)2PdCl2]-Catalyzed E/Z Isomerization of Alkenes: A Non-
Hydride Binuclear Addition−Elimination Pathway. Angew. Chem., Int.
Ed. 2011, 50, 9602−9606.
̌
2133. (g) Gehrtz, P. H.; Geiger, V.; Schmidt, T.; Srsan, L.; Fleischer,
I. Cross-Coupling of Chloro(hetero)arenes with Thiolates Employing
a Ni(0)-Precatalyst. Org. Lett. 2019, 21, 50−55.
(9) (a) Xiao, W.-J.; Vasapollo, G.; Alper, H. Highly Regioselective
Thiocarbonylation of Conjugated Dienes via Palladium-Catalyzed
Three-Component Coupling Reactions. J. Org. Chem. 2000, 65,
4138−4144. (b) Xiao, W.-J.; Alper, H. Highly Stereoselective
Palladium-Catalyzed Dithiocarbonylation of Propargylic Mesylates
with Thiols and Carbon Monoxide. J. Org. Chem. 2005, 70, 1802−
1807. (c) Burhardt, M. N.; Taaning, R. H.; Skrydstrup, T. Pd-
Catalyzed thiocarbonylation with stoichiometric carbon monoxide:
Scope and applications. Org. Lett. 2013, 15, 948−951. (d) Burhardt,
M. N.; Ahlburg, A.; Skrydstrup, T. Palladium-Catalyzed Thiocarbo-
nylation of Aryl, Vinyl, and Benzyl Bromides. J. Org. Chem. 2014, 79,
11830−11840. (e) Hirschbeck, V.; Gehrtz, P. H.; Fleischer, I.
Regioselective Thiocarbonylation of Vinyl Arenes. J. Am. Chem. Soc.
2016, 138, 16794−16799.
̃
(10) (a) Weïwer, M.; Coulombel, L.; Dunach, E. Regioselective
indium(iii) trifluoromethanesulfonate-catalyzed hydrothiolation of
́
non-activated olefins. Chem. Commun. 2006, 332−334. (b) Kucinski,
́
K.; Pawluc, P.; Hreczycho, G. Scandium(III) Triflate-Catalyzed anti-
Markovnikov Hydrothiolation of Functionalized Olefins. Adv. Synth.
Catal. 2015, 357, 3936−3942. (c) Kristensen, S. K.; Laursen, S. L. R.;
Taarning, E.; Skrydstrup, T. Ex Situ Formation of Methanethiol:
Application in the Gold(I)-Promoted Anti-Markovnikov Hydro-
thiolation of Olefins. Angew. Chem., Int. Ed. 2018, 57, 13887−
13891. (d) Tamai, T.; Fujiwara, K.; Higashimae, S.; Nomoto, A.;
Ogawa, A. Gold-Catalyzed Anti-Markovnikov Selective Hydro-
thiolation of Unactivated Alkenes. Org. Lett. 2016, 18, 2114−2117.
(11) (a) Griesbaum, K. Problems and Possibilities of the Free-
Radical Addition of Thiols to Unsaturated Compounds. Angew.
Chem., Int. Ed. Engl. 1970, 9, 273−287. (b) Biermann, U.; Metzger, J.
O. Regioselectivity of Radical Addition of Thiols to 1-Alkenes. Eur. J.
Org. Chem. 2018, 2018, 730−734. (c) Sinha, A. K.; Equbal, D. Thiol−
Ene Reaction: Synthetic Aspects and Mechanistic Studies of an Anti-
Markovnikov-Selective Hydrothiolation of Olefins. Asian J. Org. Chem.
2019, 8, 32−47.
(12) (a) Hoyle, C. E.; Bowman, C. N. Thiol-Ene Click Chemistry.
Angew. Chem., Int. Ed. 2010, 49, 1540−1573. (b) Dondoni, A.; Marra,
A. Recent applications of thiol-ene coupling as a click process for
glycoconjugation. Chem. Soc. Rev. 2012, 41, 573−586. (c) Lowe, A. B.
Thiol-ene ″click″ reactions and recent applications in polymer and
materials synthesis: a first update. Polym. Chem. 2014, 5, 4820−4870.
́
(13) (a) Cabrero-Antonino, J. R.; Leyva-Perez, A.; Corma, A. Iron-
Catalysed Markovnikov Hydrothiolation of Styrenes. Adv. Synth.
Catal. 2012, 354, 678−687. (b) Savolainen, M. A.; Wu, J.
Markovnikov-Selective Hydrothiolation of Styrenes: Application to
the Synthesis of Stereodefined Trisubstituted Olefins. Org. Lett. 2013,
15, 3802−3804. (c) Ma, H.; Ren, X.; Zhou, X.; Ma, C.; He, Y.;
Huang, G. Palladium and copper co-catalyzed Markovnikov hydro-
E
Org. Lett. XXXX, XXX, XXX−XXX