Regio- and Stereoselective Thianthrenation of Olefins To Access Versatile Alkenyl Electrophiles

Article abstract of DOI:10.1002/anie.201914215

Herein, we report a regioselective alkenyl electrophile synthesis from unactivated olefins that is based on a direct and regioselective C?H thianthrenation reaction. The selectivity is proposed to arise from an unusual inverse-electron-demand hetero-Diels–Alder reaction. The alkenyl sulfonium salts can serve as electrophiles in palladium- and ruthenium-catalyzed cross-coupling reactions to make alkenyl C?C, C?Cl, C?Br, and C?SCF₃ bonds with stereoretention.

Full text of DOI:10.1002/anie.201914215

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Accepted Article
Title: Regio- and Stereoselective Thianthrenation of Olefins to Access
Versatile Alkenyl Electrophiles
Authors: Tobias Ritter, Junting Chen, Jiakun Li, Matthew Plutschack,
and Florian Berger
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201914215
Angew. Chem. 10.1002/ange.201914215
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Angewandte Chemie International Edition
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COMMUNICATION
Regio- and Stereoselective Thianthrenation of Olefins to Access
Versatile Alkenyl Electrophiles
Junting Chen, Jiakun Li, Matthew B. Plutschack, Florian Berger, and Tobias Ritter*
[
8]
Abstract: Here we report a regioselective alkenyl electrophile
synthesis from unactivated olefins via a direct and regioselective C–
H thianthrenation reaction. The selectivity is proposed to arise from
an unusual inverse electron demand hetero Diels-Alder reaction.
The alkenyl sulfonium salts can serve as electrophiles for palladium
and ruthenium catalyzed cross-coupling reactions to make alkenyl
other metal species, followed by treatment with electrophilic
halogen sources. Methods starting from alkynes can afford
alkenyl halides in one step, although they are less widely used
considering the smaller availability of alkynes when compared to
[
8]
alkenes. Other frequently used methods like the Takai- and
Wittig olefination reactions often give E/Z mixtures starting from
aldehydes or ketones.
pseudo)halides directly from widely available alkenes, but
functionalizations of alkenes commonly deliver
hydrofunctionalized or vicinal difunctionalized alkanes.
Modern olefin metathesis catalysts can sometimes access the Z
isomers of alkenyl halides through cross metathesis, and also
E alkenyl halides in some cases when bulky substituents are
[
9]
C–C, C–Cl, C–Br and C–SCF
3
bonds stereo-retentively.
It is desirable to access alkenyl
(
Olefins are among the most useful building blocks in organic
synthesis, but the direct synthesis of alkenyl electrophiles from
[10]
[
1]
2
olefins is an unsolved problem. While olefins display C(sp )–H
3e
bonds like arenes, their reactivity is distinct from arenes when
2
treated with electrophiles: arenes undergo electrophilic C(sp )–H
[11]
present in the starting material.
available directly from C(sp )–H functionalization of alkenes,
Alkenyl nucleophiles are
substitution, while olefins typically undergo addition reactions
2
[
2]
like dihalogenation to generate dihaloalkanes. Despite the
synthetic utility of alkenyl electrophiles, general direct and
[12]
[13]
such as alkenyl silane
and boronate.
and alkenyl nitrile
Michael acceptors
[14]
[15]
such as nitroolefin
can also be
2
regioselective functionalization of olefins via C(sp )–H
synthesized from alkenes. Procter disclosed the synthesis of
alkenyl sulfoniums via an interrupted Pummerer approach, but
the reaction is limited to styrene-like substrates.
reported a directed C(sp )–H functionalization to make alkenyl
iodides that bear a picolinamide directing group.
synthesis of versatile alkenyl electrophiles from simple olefins
via C(sp )–H functionalization is as of yet unknown.
we fill this gap, and showcase the utility of the alkenyl sulfonium
electrophiles in several cross-coupling reactions. The chemistry
differs conceptually from prior art due to an unusual mechanism
of olefin functionalization that sets the chemistry apart from
arene thianthrenation and other syntheses of alkenyl sulfoniums.
[
3]
substitution to access them is not yet known. Herein, we report
regio- and stereoselective method to afford alkenyl
a
[16]
Carreira
2
electrophiles directly from unactivated alkenes by C(sp )–H
substitution (Scheme 1). The high stereoselectivity may be the
consequence of an unusual inverse electron demand hetero
Diels-Alder reaction with a previously unused dicationic aromatic
thianthrene dication. The resulting alkenyl sulfonium salts are
versatile electrophiles for palladium- and ruthenium-catalyzed
cross-coupling reactions.
2
[17]
The direct
2
[12-16,18]
Here
2
We have recently published a site-selective aromatic C(sp )–
H functionalization reaction via in situ activation of thianthrene-
[
19a]
S-oxides with trifluoroacetic anhydride.
The formed aryl
thianthrenium salts are used as aryl electrophiles to synthesize
[
19a]
[19b]
[19c]
challenging bonds like aryl C–SCF
3
,
C–CF
3
,
C–N,
C–
[
19d]
[19e,f]
O,
and C–F
bonds. Extension of aromatic substitution
chemistry to olefins is generally not successful because olefins
typically react with electrophiles by addition. Thianthrene radical
2
Scheme 1. Stereoselective C(sp )–H thianthrenation of olefins;
TT=thianthrenium.
[
20]
cation addition to olefins has been explored. In contrast to this
addition chemistry and our previous arene substitution; we
disclose here data that supports a distinct mechanism for alkene
substitution that allows for the selective synthesis of alkenyl
sulfonium salts from thianthrene-S-oxide.
Alkenyl halides, especially alkenyl bromides and iodides, are
widely used alkenyl electrophiles for cross-coupling and other
[4]
reactions. Their syntheses often require multi-step sequences,
for instance, dibromination of alkenes followed by the elimination
The reaction is straightforward to execute: alkene (1.00
equiv.) and thianthrene-S-oxide (1) (1.03 equiv.) are dissolved in
anhydrous acetonitrile under ambient atmosphere, followed by
[5]
of HBr under harsh conditions, or the prior synthesis of alkenyl
[
6]
[7]
nucleophiles, such as alkenyl boronates, alkenyl silanes, or
sequential
addition
of
trifluoroacetic
anhydride
and
trifluoromethanesulfonic acid with cooling. The reaction is
complete within less than two hours. The products can be
purified by column chromatography (Table 1).
[
a]
J. Chen, Dr. J. Li, Dr. M. B. Plutschack, Dr. F. Berger, Prof. Dr. T.
Ritter
Max-Planck-Institut für Kohlenforschung
Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany)
E-mail: ritter@mpi-muelheim.mpg.de
Supporting information for this article is given via a link at the end of
the document.
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COMMUNICATION
2
a
Table 1. Regioselective C(sp )–H Thianthrenation of Unactivated Alkenes.
(
a) 0.500 mmol scale, 1.03 equiv. thianthrene-S-oxide (1), 3.00 equiv. trifluoroacetic anhydride (TFAA), 1.20 equiv. trifluoromethanesulfonic acid (HOTf). Isolated
1
yields. E/Z ratios were determined by H-NMR. (b) 2.40 equiv. of HOTf was used to obtain better E/Z ratio. (c) The alcohol was partially acylated during the
reaction (see Supporting Information). (d) 1.20 equiv. HBF •Et O instead of HOTf was used to obtain better E/Z ratio. (e) Reaction was performed on 3.00 mmol
scale. (f) Cyclododecene starting material used as mixture of isomers (E/Z ≈ 1/2, see Supporting Information). (g) E/Z ratio is not applicable. (h) 1.20 equiv.
4
2
4
HBF •Et
2
O instead of HOTf was used to obtain higher yields. (i) 2.40 equiv. of HOTf was used to obtain higher yields.
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COMMUNICATION
For all α-olefins, the E-alkenyl sulfonium salts were obtained
as major products, often without detectable Z isomers, when
analyzed by NMR spectroscopy. Functionalization of internal
alkenes proceeded with retention of the double bond geometry
for both E (2, 22) and Z (3, 23) olefins. Steric bulk in the allylic
to the olefin, followed by single electron oxidation and
subsequent cyclization to the bicyclic adducts, but oxidation and
cyclization would need to occur faster than bond rotation around
the C–C single bond to account for the observed selectivity. In
addition, reaction of thianthrene radical cations with olefins can
position does not interfere with productive functionalization (6, 7). afford bis-adducts, with two thianthrene radical cations reacting
[
20]
Functional groups like imides (11), primary alkyl bromides (8),
alcohols (9), ethers (15, 16), amides (17), esters (26–33),
ketones (29) piperidine (30), nitro (31), sulfonamides (32),
sulfones (33), and nitrile (33) are all tolerated. Electron rich
with one olefin. Attempts to thermally induce a cycloreversion
of the cycloadduct 2-INT was not successful, possibly due to its
two formal positive charges that also prevented experiments
such as flash-vacuum-pyrolysis. Treatment of either bicycle with
mild base, such as bicarbonate, resulted in clean and high-
yielding conversion to the corresponding alkenyl sulfonium salts
2-TT and 3-TT, respectively, with complete selectivity of olefin
geometry. Stereoelectronic considerations dictate that the
elimination cannot proceed by an E2 mechanism due to the
geometry of the bicycles 2-INT and 3-INT, which prevent an
antiperiplanar arrangement of leaving group and proton. An E1
mechanism cannot be excluded but is unlikely due to the near
complete degree of fidelity of double bond geometry. Consistent
with all data is an E1cBirr mechanism where rate-determining
[
19c]
arenes can undergo aromatic substitution,
but electron-poor
(
11, 13), electron-neutral (12) and six-membered heterocyclic
arenes (26, 27, 31) are tolerated. Even bis-benzylic and allylic
3
C(sp )–H bonds (12, 13) are tolerated without double bond
[
13b,18,21]
isomerization or allylic functionalization.
Internal olefins
that are electronically biased such as enol ethers (16) are
functionalized regioselectively, as are all α-olefins, but the
[22]
regioselectivity diminishes for other 1,2-disubstituted olefins.
Trisubstituted olefins (15) on the other hand are functionalized
regioselectively. Cyclic olefins (18, 19, 20, 21) participate well.
Selective monofunctionalization is observed for dienes (5, 23, 24) deprotonation is followed by a rapid elimination.
and a triene (22), most likely due to the introduction of a cationic
substituent in an electrophilic pathway.
[
23]
To rationalize the selectivity, especially the unusually high
selectivity with respect to double bond geometry such as in 2
and 3 (Scheme 2), we attempted to gain further insight into the
reaction mechanism. When the work-up of the reaction
(
aqueous bicarbonate) was omitted, we were able to isolate and
fully characterize the two diastereomeric intermediates 2-INT
and 3-INT from E- and Z-4-octene, respectively. Both, the
cycloadducts 2-INT and 3-INT as well as the high selectivity are
consistent with an unusual [4+2] cycloaddition between olefin
and the dicationic thianthrenium dication (see Supporting
Information). To substantiate the viability of the unusual
thianthenium dication as a reaction partner, we have observed it
by cyclic voltammetry and recorded its UV-vis spectrum in an
electrical cell at constant potential (see Supporting Information).
We cannot rule out an addition of the thianthrene radical cation
2
Scheme 2. Mechanism for regioselective thianthrenation of alkenyl C(sp )–H
bonds.
Table 2. Derivatizations of Alkenyl Thianthrenium Salts.
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COMMUNICATION
(
a) CyclopropylZnBr (3.0 equiv.), Pd(PPh
Pd(PPh Cl
Cp*Ru(MeCN)
Cp*Ru(MeCN)
3
)
2
Cl
2
(20 mol%) in THF (0.1 M). (b) Phenylacetylene (2.0 equiv.), N-methylmorpholine (2.0 equiv.), CuI (25 mol%),
)
3 2
2
(10 mol%) in THF (0.1 M). (c) 2-Vinylnaphthalene (2.0 equiv.), K
2
CO
(1 mol%) in THF (0.1 M). (e) LiBr (1.5 equiv.), [Cp*Ru(MeCN)
(5 mol%) in THF (0.1 M).
3
(2.5 equiv.), Pd
2 3
(dba) (10 mol%) in DMF (0.1 M). (d) LiCl (1.5 equiv.),
+
–
[
[
3
]PF
6
6
3
]PF (5 mol%) in THF (0.1 M). (f) [Me N ][ SCF ] (1.2 equiv.),
6
4
3
3
]PF
[
19]
As their aromatic counterparts,
the alkenyl thianthrenium
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salts serve as excellent electrophiles in follow up
transformations and thus differ from other alkenyl sulfonium salts
that have narrower reactivity (Table 2). Palladium-catalyzed
cross coupling reactions generally proceed with retention of the
double bond geometry (34, 35, 36, and see Supporting
Information). The alkenyl thianthrenium salts also serve as
suitable electrophiles for ruthenium-based catalysis, which
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regio- and stereoselectively for a large variety of olefin classes.
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could proceed via an unusual inverse electron demand
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Keywords: alkenes • regioselective • C–H functionalization •
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Entry for the Table of Contents
COMMUNICATION
Junting Chen, Jiakun Li, Matthew B.
Plutschack, Florian Berger, and Tobias
Ritter*
Page No. – Page No.
Regio- and Stereoselective
Thianthrenation of Olefins to Access
Versatile Alkenyl Electrophiles
We report a regioselective synthesis of sulfonium-based alkenyl electrophiles
directly through C–H functionalization of simple olefins. The alkenyl sulfonium salts
participate in palladium catalyzed cross coupling and ruthenium catalyzed
(
pseudo)halogenation reactions.
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