SUPPORTING INFORMATION
Synthesis of Enyne and Vinyl Sulfoxides followed by functionalization via Pummerer
rearrangement and Suzuki-Miyaura cross coupling reaction
Frederico B. Souza, Anwar Shamim, Luiz M. A. Argomedo, Daniel C. Pimenta,
Hélio A. Stefani*
TABLE OF CONTENTS
General considerations
1
HNMR and 13CNMR spectra
02
03
1
General Experimental Section. 1-Alkynyl p-Toluyl sulfoxides 3 was prepared according to the reference [20].
Synthesis of 1-sulfinyl alkenyl tributylstannanes 5 was prepared according to he reference [23]. Synthesis of iodo1-sulfinyl akenes 6 was prepared according to the reference [24]. Proton nuclear magnetic resonance spectra (1H NMR)
were obtained at 300 MHz. Spectra were recorded in a CDCl3 solution. Chemical shifts are reported in ppm, referenced
to the solvent peak of CDCl3 or tetramethylsilane (TMS) as the external reference. Data are reported as follows:
chemical shift (), multiplicity, coupling constant (J) in Hertz and integrated intensity. Carbon-13 nuclear magnetic
resonance spectra (13C NMR) were obtained at 75 MHz. Chemical shifts are reported in ppm, referenced to the solvent
peak of CDCl3. Abbreviations to denote the multiplicity of a particular signal are s (singlet), d (doublet), t (triplet), q
(quartet), quint (quintet), sex (sextet) and m (multiplet). 1H NMR and 13C NMR spectra were recorded on spectrometer
Bruker DPX 300. High-resolution mass spectra were obtained using a high-resolution ESI-TOF mass spectrometer
Shimadzu LCMS-IT-TOF. Specific rotations were recorded using chloroform as solvent in different concentrations
how is showed in each compound on a polarimeter Anton Paar MCP 200. Column chromatography was performed
using silica gel (230-400 mesh). Thin layer chromatography (TLC) was performed using silica gel UV254, 0.20 mm
thickness. For visualization, TLC plates were either placed under ultraviolet light, or stained with iodine or acidic
vanillin solution. Tetrahydrofuran was dried and purified by distillation from sodium with benzophenone as the
indicator. All other solvents were ACS or HPLC grade unless otherwise noted. Air and moisture-sensitive reactions
were conducted in flame-dried or oven-dried glassware equipped with tightly fitted rubber septa and under a positive
atmosphere of dry nitrogen. Reagents and solvents were handled using standard syringe techniques. Temperatures
above room temperature were maintained by the use of a mineral oil bath with an electrically heated coil connected to
a controller.
2
(R,E)-1-((2-butyloct-1-en-3-yn-1-yl)sulfinyl)-4-methylbenzene (4a)
3
(R,E)-1-methyl-4-((2-propylhept-1-en-3-yn-1-yl)sulfinyl)benzene (4b)
4
(R,E)-1-((2,4-dicyclopropylbut-1-en-3-yn-1-yl)sulfinyl)-4-methylbenzene (4c)
5
(R,E)-1-methyl-4-((2-pentylnon-1-en-3-yn-1-yl)sulfinyl)benzene (4d)
6
(R,E)-1-((2-hexyldec-1-en-3-yn-1-yl)sulfinyl)-4-methylbenzene (4e)
7
(R,E)-1,1'-(4-(p-tolylsulfinyl)but-3-en-1-yne-1,3-diyl)dicyclohex-1-ene (4f)
8
(R,Z)-(((4-((p-tolylsulfinyl)methylene)pent-2-yne-1,5-diyl)bis(oxy))bis(methylene))dibenzene (4g)
9
(R,Z)-(4-((p-tolylsulfinyl)methylene)pent-2-yne-1,5-diyl)bis(phenylsulfane) (4h)
10
(S,Z)-1-methoxy-4-(1-(p-tolylsulfinyl)hex-1-en-1-yl)benzene (8a)
11
(S,Z)-3-(1-(p-tolylsulfinyl)hex-1-en-1-yl)thiophene (8b)
12
(S,Z)-2-(1-(p-tolylsulfinyl)hex-1-en-1-yl)naphthalene (8c)
13
(S,Z)-1-(4-(1-(p-tolylsulfinyl)hex-1-en-1-yl)phenyl)ethanone (8d)
14
(S,Z)-1,3-dimethoxy-2-(1-(p-tolylsulfinyl)hex-1-en-1-yl)benzene (8e)
15
(S,Z)-1-(1-(p-tolylsulfinyl)hex-1-en-1-yl)-3,5-bis(trifluoromethyl)benzene (8f)
16
(S,Z)-ethyl(4-(1-(p-tolylsulfinyl)hex-1-en-1-yl)phenyl)sulfane (8h)
17
(S,Z)-1-bromo-4-(1-(p-tolylsulfinyl)hex-1-en-1-yl)benzene (8j)
18
(S,Z)-4-(1-(p-tolylsulfinyl)hex-1-en-1-yl)benzoic acid (8k)
19
(S,Z)-4-(1-(p-tolylsulfinyl)hex-1-en-1-yl)benzonitrile (8l)
20
(S,Z)-3-(1-(p-tolylsulfinyl)hex-1-en-1-yl)aniline (8m)
21
(S,Z)-1-methoxy-3-(1-(p-tolylsulfinyl)hex-1-en-1-yl)benzene (8n)
22
2-butyl-2-(p-tolylthio)oct-3-ynal (9a)
23
2,4-dicyclopropyl-2-(p-tolylthio)but-3-ynal (9c)
24
5-(phenylthio)-2-((phenylthio)methyl)-2-(p-tolylthio)pent-3-ynal (9e)
25
2,4-di(cyclohex-1-en-1-yl)-2-(p-tolylthio)but-3-ynal (9f)
26