Pd-Catalyzed Cyanoselenylation of Internal Alkynes: Access to Tetrasubstituted Selenoenol Ethers

Article abstract of DOI:10.1021/acs.orglett.0c01582

The intra- and intermolecular synthesis of selenium-substituted acyclic and heterocyclic acrylonitrile derivatives is presented. The 1,2-difunctionalization of several internal alkynes substituted not only by aliphatic and aromatic residues but also by heteroelements is realized by the Pd-catalyzed activation of aromatic and aliphatic selenocyanates. A high functional group tolerance allows straightforward access to a broad scope of tetrasubstituted olefins. X-ray studies of some products reveal noncovalent chalcogen-chalcogen interactions between oxygen and selenium.

Full text of DOI:10.1021/acs.orglett.0c01582

pubs.acs.org/OrgLett
Letter
Pd-Catalyzed Cyanoselenylation of Internal Alkynes: Access to
Tetrasubstituted Selenoenol Ethers
̈
̈
Marcel Burger, Sebastian H. Rottger, Maximilian N. Loch, Peter G. Jones, and Daniel B. Werz*
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ABSTRACT: The intra- and intermolecular synthesis of selenium-substituted acyclic and heterocyclic acrylonitrile derivatives is
presented. The 1,2-difunctionalization of several internal alkynes substituted not only by aliphatic and aromatic residues but also by
heteroelements is realized by the Pd-catalyzed activation of aromatic and aliphatic selenocyanates. A high functional group tolerance
allows straightforward access to a broad scope of tetrasubstituted olefins. X-ray studies of some products reveal noncovalent
chalcogen−chalcogen interactions between oxygen and selenium.
he significance of tetrasubstituted olefins is demonstrated
by their manifold applications, e.g. in functional
leading to highly (hetero)substituted thioenol ethers.19 The
versatility of this atom-economic addition of aromatic and
aliphatic thiocyanates to internal alkynes was demonstrated by
a broad range of thioacrylonitrile derivatives (Scheme 1). This
process could even be extended to a cascade, leading to several
T
materials1 or in effective pharmaceuticals.2 Chemists continue
to intensify their research in this field.3 Various methods have
been developed to simplify the synthetic access to different
substitution patterns.4,5 In particular, Pd-catalyzed reactions,
because of their generality and tolerance toward many
functional groups, are a powerful tool to release the inherent
reactivity of triple bonds.6 For example, Larock published a
regio- and stereoselective route to triphenylethylene derivatives
that are parent compounds of some nonsteroidal drugs.7
Furthermore, the synthesis of overcrowded double bonds, the
essential molecular subunits in molecular switches and motors,
is as important as ever. For this purpose, highly efficient
cascade processes have increasingly become the method of
choice.8 Such domino reactions, as they are also called,
combine economic and ecological advantages with synthetic
elegance.9 Complex skeletons are built up in a single synthetic
step that involves the formation of multiple C−C bonds.10
In several investigations, our group has shown the
tremendous power of this concept.11 Besides classical syn-
carbopalladations,12 the incorporation of a formal anti-
carbopalladation enabled the synthesis of one or more
tetrasubstituted double bonds embedded in various polycyclic
compounds.13,14 Such anti-carbopalladations of C−C triple
bonds have also been employed to access tetrasubstituted
double bonds with at least one heteroatom as a substituent, as
demonstrated by the preparation of a series of enol ethers15
and enamines.16 Nevertheless, the tetrasubstitution of an
alkene with the maximum number of heterosubstituents
remains underdeveloped, even though some beautiful work
has been reported in recent years.17,18
Scheme 1. Overview of Pd-Catalyzed
Cyanochalcogenylation Reactions
Received: May 8, 2020
In our earlier work, we demonstrated that Pd-catalysis is the
key to conducting a cyanosulfenylation of internal alkynes,
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conjugated tetrasubstituted C−C double bonds, with the
delivery of the cyanide as the terminating step. Based on these
insights and other reports on the Pd-catalyzed activation of
chalcogenocyanates,20,21 we asked ourselves whether an
extension of this reactivity to the higher homologues, the
corresponding selenocyanates, might be feasible. Besides some
interesting protocols for the synthesis of highly substituted
vinyl selenides,23 such an approach would easily grant access to
tetrasubstituted selenoenol ethers (Scheme 1). Furthermore,
this would emphasize the synthetic benefit of selenium
compounds, whose importance is intensely discussed in
literature.22
In a first series of experiments, using the catalytic systems of
our previous study on the Pd-catalyzed cyanothiolation, we
found that the transformation of 1a to the tetrahydroseleno-
phene derivative 2a proceeded smoothly with an excellent
yield of 93%. Ideal conditions include 10 mol % of Pd2(dba)3
as precatalyst and 20 mol % of XantPhos as ligand in a closed
reaction vial with toluene as solvent at 160 °C.24 Subsequently,
we synthesized a variety of selenocyanates 1 tethered to alkyne
moieties in order to explore the scope and limitations of this
1,2-addition process. Sterically demanding, electron-rich
residues, and also electron-poor aromatic and heteroaromatic
residues, at the alkyne terminus were well tolerated and
afforded products 2b−2e in 64−94% yield (Scheme 2), which
withdrawing CF3 group as the terminus, albeit in lower yield
(2h, 29%). In this case, two diastereomers were found in a 1:1
ratio. Such a strong polarization leads to some extent to an
isomerization of the exocyclic double bond, as we had already
observed in our previous cyanosulfenylation products.19
Furthermore, we subjected substrates with a conjugated triple
bond to the reaction conditions. A naphthyl residue (2k)
allowed the formation of the product in only 11% yield,
whereas a p-chlorophenyl substituent provided isoselenochro-
mene 2l in 84% yield.
Our next goal was the transformation of aromatic
selenocyanates 3 to the corresponding products 4 (Scheme
3). We realized that Pd(PPh3)4 and SPhos as ligand proved to
Scheme 3. Intramolecular Cyanoselenylation with Aromatic
a
Selenocyanates
Scheme 2. Intramolecular Cyanoselenylation with Aliphatic
a
Selenocyanates
a
General reaction conditions: substrate 3 (1.0 equiv), solvent (20
b
mM). Yields represent isolated compounds. Reaction time: 12 h.
be superior to the catalytic system applied for aliphatic
selenocyanates. The reaction with propargylic tethers in ortho-
position furnished the six-membered heterocycles 4a−4c in
good to quantitative yields. The elongation of the linker by one
methylene unit allowed the synthesis of the seven-membered
oxaselenepine derivative 4d in a good yield of 76%. The
conversion of a methyl propiolate led to an isomeric mixture of
4e (34%); the E/Z isomerization is facilitated because the
second acceptor in geminal position to the nitrile further
weakens the double bond. The crystal structure of the (E)-
isomer of 4e is shown in Figure 1. Additionally, we were able
to crystallize the selenazin derivative 4f, which was obtained in
a good yield of 62%.
As mentioned at the beginning, reports of tetrasubstituted
double bonds functionalized with several heteroatoms are rare.
Furthermore, it is often difficult to access them in a few, let
alone one, synthetic step(s). Our method allows the direct and
diastereoselective access to such moieties. To demonstrate this,
we synthesized four examples based on the five-membered
exocyclic selenoenol ether backbone (Scheme 4).
a
General reaction conditions: substrate 1 (1.0 equiv), solvent (20
b
mM). Yields represent isolated compounds. Large scale (1.0 mmol,
99% yield). Reaction temperature: 120 °C.
c
is in a comparable range as for the sulfur analogues.19 In a
series with aliphatic substituents, the compounds 2f (96%) and
2i (82%) were obtained in excellent yields, whereas the
formation of 2g was limited by the bulkier tert-butyl group.
The fact that the three-membered ring system stays intact
demonstrates that no radical processes are involved. Product
2j, with a THP-protected alcohol distanced by a methylene
unit, was prepared successfully in 85% yield. The trans-
formation was possible even with the strongly electron-
Silyl groups are predestined as a second heterosubstituent at
the terminus of the alkyne unit. Using a TBS group, we
generated the fully substituted olefin 6a in a high yield of 89%.
The structure was unequivocally confirmed by X-ray structure
analysis. Obviously, the attachment of chalcogens such as
sulfur and selenium in α-position to the alkyne paved the way
B
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Scheme 5. Intermolecular Cyanoselenylation of Symmetric
a
and Unsymmetric Alkynes
Figure 1. Noncovalent intramolecular Se···O interactions.
Scheme 4. Intramolecular Cyanoselenylation of
a
Heterosubstituted Triple Bonds
a
General reaction conditions: substrates 7 (1.0 equiv) and 8 (2.0
equiv), solvent (100 mM). Yields represent isolated compounds.
proceeded with varying degrees of success. First, we
investigated whether it is possible to use a 1,3-diyne unit for
this addition. Whereas we did not observe any reaction with
PhSeCN, we found traces of the desired product with the 4-
methoxy derivative. Only the very electron-rich 3,4,5-
trimethoxyphenyl selenocyanate eventually enabled the for-
mation of enyne 9e, albeit in a low, but isolable yield. In
contrast, the strongly polarized acetylene carboxylic acid ester
provided the push−pull-substituted acrylate 9f in a yield of
50%; however, the expected syn-adduct was not obtained, but
instead its anti-diastereomer. The configuration was deter-
mined by X-ray crystallography. The example of 1-phenyl-1-
propyne shows that a nonpolarized conjugated triple bond is
again difficult to convert; the corresponding product 9g was
obtained only in low yield and as a regioisomeric mixture (3:1)
because of the lack of electronic and steric differentiation of
the two acetylenic carbons.
In several of the X-ray crystal structures that we obtained
during this study, we noticed short intramolecular Se···O
contacts. Such noncovalent chalcogen−chalcogen interactions,
reported in several publications, have been well studied and
exploited in crystal engineering and more recently in
organocatalysis.25−27 The close Se···O contacts of the oxy-
gen-containing selenoenol ethers 4e, 9b, and 9f are shown in
Figure 1; the distances range from 2.68 to 2.81 Å, which is
significantly less than the sum of the van der Waals radii of
oxygen and selenium (3.40 Å).27 The angle O−Se−C ranges
from 164° to 172°, demonstrating the favored directionality of
this weak, but significant interaction, which might also be an
additional driving force for the isomerization of the olefins (4e
and 9f).
a
General reaction conditions: substrate 5 (1.0 equiv), solvent (20
mM). Yields represent isolated compounds.
for two further examples, 6b and 6c, obtained in a moderate
yield of 54−56%. The combination of selenium/nitrogen in
trans-position across a double bond was realized by the
synthesis of alkene 6d starting from the corresponding
ynamide. An X-ray crystal structure clearly shows the
anticipated substitution pattern.
Finally, we were interested in the intermolecular reaction of
a selenocyanate 7 with an internal alkyne 8 (Scheme 5). We
used commercially available phenyl selenocyanate and 3-
hexyne to obtain insight into this challenging transformation.
Using the standard catalytic system (cf. Scheme 2), we
observed the formation of 9a, but only in a yield of less than
10%. To increase the yield, we had to suppress the formation
of diphenyldiselenide as the major byproduct. One reason for
this is the easier oxidation of selenium compared to sulfur.
Disulfide formation was scarcely observed for the intermo-
lecular cyanothiolation.19 With 2 equiv of alkyne we were able
to raise the yield of 9a to 55%. Unluckily, these conditions did
not prove suitable for the reaction of further selenocyanates
(electron-poor and electron-rich aromatic, or aliphatic
derivatives) with 3-hexyne. In all cases we isolated the
products 9b−9d, but in low yields ranging from 6% to 17%.
Again, the respective diselenides were found to be the major
products when using these starting materials. The addition of
selenocyanate derivatives to unsymmetric alkynes also
In summary, we have demonstrated the versatility of Pd-
catalyzed cyanoselenylation for the synthesis of tetrasubsti-
tuted olefins. This methodology allows the addition of both
aromatic and aliphatic selenocyanates to diversely function-
alized alkynes. The intramolecular version of this methodology
is as efficient as the previously reported cyanothiolation,
whereas the intermolecular reaction is rather limited. However,
the transformation provides access to tetrasubstituted acyclic
selenoethers and to five-, six-, and seven-membered hetero-
C
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.0c01582.
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General experimental details and procedures; crystallo-
graphic data for 1k (CCDC 1998935), 2c (CCDC
1998936), anti-4e (CCDC 1998937), 4f (CCDC
1998938), 6a (CCDC 1998939), 6d (CCDC
1998940), 9b (CCDC 1998941), and 9f (CCDC
1998942) (PDF)
Accession Codes
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catalyzed cross-coupling reactions and more; de Meijere, A., Oestreich,
CCDC 1998935−1998942 contain the supplementary crys-
tallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
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AUTHOR INFORMATION
Corresponding Author
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̈
Daniel B. Werz − Technische Universitat Braunschweig, Institut
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2019, 25, 3010−3013. (b) Liu, X.-W.; Li, S.-S.; Dai, D.-T.; Zhao, M.;
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fu
̈
r Organische Chemie, 38106 Braunschweig, Germany;
orcid.org/0000-0002-3973-2212; Email: d.werz@tu-
̀
braunschweig.de
Authors
Marcel Bu
̀
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̈
rger − Technische Universitat Braunschweig, Institut
̈
fur Organische Chemie, 38106 Braunschweig, Germany
Sebastian H. Rottger − Technische Universitat Braunschweig,
Institut fur Organische Chemie, 38106 Braunschweig, Germany
Maximilian N. Loch − Technische Universitat Braunschweig,
Institut fur Organische Chemie, 38106 Braunschweig, Germany
Peter G. Jones − Technische Universitat Braunschweig, Institut
fur Anorganische und Analytische Chemie, 38106
̈
̈
̈
̈
̈
̈
(7) Zhou, C.; Larock, R. C. J. Org. Chem. 2005, 70, 3765−3777.
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Angew. Chem., Int. Ed. 2015, 54, 10317−10321. (c) Tietze, L. F.;
̈
̈
Braunschweig, Germany
Complete contact information is available at:
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Hungerland, T.; Eichhorst, C.; Du
Chem., Int. Ed. 2013, 52, 3668−3671. (d) Tietze, L. F.; Hungerland,
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The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We are grateful to the TU Braunschweig for funding. M.B.
thanks Adrian Bauschke (TU Braunschweig) for his support.
■
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