Meyer-Schuster-type rearrangement for the synthesis of α-selanyl-α,β-unsaturated thioesters

Article abstract of DOI:10.1039/d0cc07019j

A new approach to prepare α-selanyl-α,β-unsaturated thioesters from propargylthioalkynes and an electrophilic selenium species is reported. Pivotal is the intermediacy of a sulfur-stabilized vinyl cation, which is captured intramolecularly and ultimately

Full text of DOI:10.1039/d0cc07019j

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DOI: 10.1039/D0CC07019J
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Meyer-Schuster-type Rearrangement for the Synthesis of
α-Selanyl-α,β-Unsaturated Thioesters
Received 00th January 20xx,
Accepted 00th January 20xx
Lucas L. Baldassari,a Anderson C. Mantovani,a Micaela Jardim,a Boris Maryasin,b,c,* and Diogo S.
Lüdtkea,*
DOI: 10.1039/x0xx00000x
several occasions not easy to synthesize, presenting regioselectivity
problems and formation of difficult separation mixtures, leaving its
general synthesis still a challenge to synthetic chemists.
A new approach to prepare α-selanyl-α,β-unsaturated thioesters
from propargylthioalkynes and an electrophilic selenium species is
reported. Pivotal is the intermediacy of a sulfur-stabilized vinyl
cation, which is captured intramolecularly and ultimately enables
37 examples of the target compounds to be prepared in good
yields. Computational studies shed light on the nature of
intermediates in this transformation.
A. Traditional approach: acryloyl chloride and thiol
O
O
+
RSH
SR
Cl
regioselectivity issues
α,β-Unsaturated thioesters are a class of significant molecules and
their importance is highlighted by their use in several areas, such as
polymer chemistry,1 enoyl-CoA carboxylase/reductases substrate in
enzymatic catalysis,2 and as an intermediate for the synthesis of
B. Meyer-Schuster rearrangement
O
HO
H+
R2
R1
R2
R1
commercially
important
fragrances
phenoxanol
and
useful
hydroxycitronellal.3 Indeed, this functional group is
a
C. Concept: -chalcogen-stabilized vinyl cation
Se-stabilized
synthetic building block, being a common substrate for 1,4-
additions,4 additions,5
asymmetric conjugate α-
R1
vinyl cation
trifluoromethylations,6 Diels-Alder cycloadditions,7 hydrogenations,8
intramolecular rearrangements,9 and decarbonylative reactions.10
The vast majority of the methods available for their synthesis
typically involves the use of acryloyl chlorides and thiols, a route
that commonly presents issues related to the handling of unstable
acryloyl chlorides and competing thiol 1,4-addition side reactions
(Scheme 1A).11 Other methodologies are based on the use of
carbonyl compounds12 or epoxides13 and thioacetylenes, catalyzed
by Lewis acid. Conversion of carboxylic acids into thioesters,14
ruthenium catalyzed rearrangement of propargyl sulfoxides,15 thiol
1,4-addition to alkylidene Meldrum’s acid derivatives,16 Horner17
and Wittig18 olefinations of thiophosphonates, aldol reaction
promoted by TiCl4,19 thermal decomposition of α-sulfinyl-
thioesters,20 thiocarbonylation of acetylenes with thiols and carbon
monoxide21 and thioesterification of aldehydes with disulfides
catalyzed by N-heterocyclic carbenes22 have also been reported.
Despite of the available methods, α,β-unsaturated thioesters are on
SeR2
R1
SeR2
ref 26
H
O
R1
SeR2
SPh
TfOH cat
R1
SeR2
+ Ph2SO
D. This work: -unsaturated thioester synthesis
HX
HX
propargyl
thioalkyne
S-stabilized
SR
SR
vinyl cation
E
R1
O
R3SeI
HO
R1
R2
SR
SR
H
R2
SeR3
a.
Instituto de Química, Universidade Federal do Rio Grande do Sul, UFRGS, Av.
Bento Gonçalves 9500, 91501-970, Porto Alegre, RS, Brazil. E-mail:
dsludtke@iq.ufrgs.br
Institute of Organic Chemistry, University of Vienna, WähringerStraße 38,
R1
R1
O
b.
- H+
R2
R3Se
O
R2
1090 Vienna, Austria.
Institute of Theoretical Chemistry, University of Vienna, WähringerStraße 17,
SR
c.
R3Se
SR
1090 Vienna, Austria. E-mail: boris.maryasin@univie.ac.at
Electronic Supplementary Information (ESI) available: Experimental procedures,
analytical data, copies of NMR spectra, and computational details. See
DOI: 10.1039/x0xx00000x
Scheme 1. Key precedents and this work
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One elegant method for the synthesis of α,β-unsaturated the reaction conditions. It’s worth pointing out thatVcieowmArptiocluenOdnlin7e,
compounds is the Meyer-Schuster rearrangement of propargyl bearing a bulky iso-propyl group at the orthoDOpIo: s1i0t.i1o0n39w/Das0CoCb0ta70in1e9dJ
acetylenes to the corresponding enones (Scheme 1B).23,24
in 84% isolated yield.
Recently, our research group has been studying the potential use of Table 1. Optimization of the reaction conditionsa
heteroatom-substituted alkynes atoms in the stabilization of vinyl
Me
O
HO
PhSeI, base
solvent, t (h)
cations and their reactivity towards
a number of different
SMe
reactions.25 In particular, we have reported the use of
selenoalkynes for the synthesis of α-arylated selenol esters in a
redox-neutral oxyarylation (Scheme 1C).26 In continuation of our
studies, we hypothesized that the concept of vinyl cation
stabilization could be extended to propargyl thioalkynes, which
would be suitable substrates for electrophilic activation.27
Therefore, an ensuing sulfur-stabilized vinyl cation would result
from the reaction of the alkyne with an appropriate soft selenium
electrophile (e.g. PhSeX). This intermediate might then be
intercepted by an intramolecular nucleophilic attack of oxygen,
leading to the formation of an oxetene ring, which would then
decompose, delivering the final α-selanyl-α,β-unsaturated
thioesters in a Meyer-Schuster-type rearrangement (Scheme 1D).
Besides the above-mentioned utility of α,β-unsaturated thioesters
organic selenium compounds, including vinyl selenides, have found
widespread application in several areas of science, including organic
synthesis, material sciences, and pharmacology.28 Therefore, mild
methods that are able to deliver functionalized alkenes bearing an
organoselenium moiety are desirable.
Me
SMe
Me
Me
SePh
1
#
(PhSe)2
I2
Base (equiv)
Solvent, t (h)
Yield
(%)b
39
64
61
70
NR
67
40
29
44c
75d
80d
88e
(equiv)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.5
2.0
(equiv)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.5
2.0
1
2
3
4
5
6
7
8
9
-
CH2Cl2, 3
CH2Cl2, 3
CH2Cl2, 3
CH2Cl2, 3
THF, 3
Cs2CO3 (2.0)
NaH (2.0)
Cs2CO3 (1.2)
Cs2CO3 (1.2)
Cs2CO3 (1.2)
Cs2CO3 (1.2)
Cs2CO3 (1.2)
Cs2CO3 (1.2)
Cs2CO3 (1.2)
Cs2CO3 (1.2)
Cs2CO3 (1.2)
DCE, 3
PhCH3, 24
CH2Cl2/THF, 3
CH2Cl2, 3
CH2Cl2, 16
CH2Cl2, 16
CH2Cl2, 16
10
11
12
aReaction was performed using 0.25 mmol of thioalkyne, at 25 oC. PhSeI was
generated in situ by the reaction of (PhSe)2 with I2, and after 30 min, Na2S2O3
was added to reduce the unreacted I2 bYields determined by 1H-NMR using
mesitylene as internal standard. reaction performed at 40 0C. d18% of
c
Reducing our plan to practice, we started our studies by reacting
the propargyl thioalkyne with an in situ generated selenium
electrophile. The results are summarized in Table 1. The first
attempt was performed in the absence of base, using 2 equiv. of
PhSeI (generated in situ by the reaction of 1 equiv Ph2Se2 with 1
equiv I2) as the electrophilic selenium source, and led to the
formation of the desired α-selanyl-α,β-unsaturated thioester 1 in
39% yield (entry 1). Subsequently, the influence of the use of base
in the reaction was verified. Carrying out the experiment with 2
equiv. of Cs2CO3 resulted in product 1 in 64% yield. Additional
studies have revealed that NaH is also a suitable base for promoting
the reaction (entry 3). A decrease in the amount of Cs2CO3 to 1.2
equivalents resulted in a slight increase in the yield (entry 4, 70%). A
solvent screening was performed and the best yield was obtained
using dichloromethane (entries 4–8). Increasing the temperature to
40 °C led to a drop in the yield to 44% (entry 9). Longer reaction
times proved beneficial to the reaction and an increase in the yield
was observed by keeping the reaction for 16 h (entry 10). Finally,
we have found that changing the stoichiometry from 2 to 4 equiv.
of PhSeI led to an increase in the yield of 1 (entries 10-12, 75 to 88%
yield). It is worth pointing out that the excess of the selenium
compound is recovered at the end of the reaction as Ph2Se2 and
reused. Importantly, the PhSeI electrophile is conveniently
generated in situ by the reaction of Ph2Se2 with I2, and after 30
minutes, potassium persulfate is added to reduce any remaining
molecular iodine and suppress the formation of iodinated side-
products. After establishing the optimal conditions for the α,β-
unsaturated thioester synthesis 1, we proceeded to examine the
reaction scope in respect of the propargylic thioalkynes (Scheme 2).
A number of thioacetylenes with different substitution patterns
have been studied. Variations at the R3 attached to the sulfur atom
have shown that linear alkyl chains of different sizes (1 = methyl; 2 =
n-butyl and 3 = octyl), branched alkyl chain (4), benzyl (5) and
aromatic groups bearing electron-donating (6–9) and electron-
withdrawing groups (10-14) groups have been well tolerated under
unreacted starting material. eStarting material was fully consumed after 16 h.
In addition, variations at the R1 and R2 groups were also examined.
When R1 and R2 = ethyl, the corresponding thioester 15 was
obtained in 73% yield. Cyclic moieties have also been well tolerated
and the corresponding products bearing 5-, 6- and 7-membered
rings (16-19) have been obtained in good yields. Unfortunately,
when unsubstituted propargyl thioacetylene was used, product 20
was not observed, despite full consumption of the starting
thioalkyne. In order to study the selectivity of the reaction,
compounds bearing different R1 and R2 substituents have been
evaluated. In these cases, albeit products 21, 22 and 23 have been
isolated in good yields, unfortunately 1:1 E/Z mixtures of have been
obtained. Importantly, the reaction is amenable to scale-up and
when the reaction was performed on a 3 mmol scale only a small
decrease in the isolated yield for product 3 was observed (82% on
0.25 mmol to 74% on a 3 mmol scale).
Aiming to study the versatility in the synthesis of α,β-unsaturated
thioesters, we then turned our attention to the scope of the
reaction with respect to the substitution pattern on selenium
(Scheme 3). When R4 group is n-butyl, the corresponding products
24-27 were isolated in good yields, for different substitution at the
remaining positions of the molecule. An electrophilic Se species
bearing a benzyl group was also tested, delivering product 28 in
74% yield. Diverse arylseleno derivatives are competent activators
and both electron-donating and electron-withdrawing groups are
suitable substituents (29-38). For example, products bearing p-Cl
(29 and 30), m-CF3 (31), o-Me (32-33), p-Me (34), 2-naphthyl (35), 1-
naphthyl (36) and p-Ph (37) were successfully obtained. Finally, the
reaction is also amenable to the use of a sulfur electrophile and
product 38 was isolated in 80% yield, highlighting the versatility of
the method for the synthesis of α,β-unsaturated thioesters with
different
chalcogen
atoms
at
the
alpha
position.
2 | J. Name., 2012, 00, 1-3
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R1
O
View Article Online
DOI: 10.1039/D0CC07019J
HO
R1
R2
Cs2CO3 (1.2 equiv)
SR3
+
PhSeI
R2
SR3
CH2Cl2, 16 h, rt
SePh
OMe
Me
O
Me
O
Me
O
Me
O
Me
O
Me
O
Me
O
Me
O
Me
SBn
SPh
Me
S
Me
Me
SMe Me
SBu Me
SC8H17
Me
S
Me
S
SePh
82%
SePh
SePh
81%
SePh
SePh
SePh
SePh
75%
SePh
65%
3
82%
5
1
2
78%
88%
6
4
7
8
(74% on 3 mmol scale)
84
F3C
%
Cl
F
Br
Et
Me
O
Me
O
Me
O
Me
O
Me
O
Me
O
Et
O
Me
S
Me
S
Me
S
Me
S
Me
S
Me
S
SC8H17
SePh
Cl
SePh
SePh
SePh
SePh
60%
OMe
SePh
SePh
73%
15
11
12
13
81%
9
10
90%
81%
78%
14
60%
H
O
Me
O
Me
O
O
Me
O
O
O
O
H
SBu
Et
SBu
Ph
SC8H17
SC8H17
SC8H17
SC8H17
SC8H17
SBu
SePh
20
SePh
21
SePh
SePh
70%
SePh
SePh
81%
SePh
65%
SePh
73%
17
18
NR
22
45%
E:Z (1:1)
19
89%
E:Z (1:1)
16
23
77%
E:Z (1:1)
Scheme 2. Scope of thioacetylenes
next stage is the cyclisation of B to generate the oxetene
intermediate C. The oxetene ring-opens via cleavage of the C-O
bond forming the intermediate D. This step, CD, is highly
exergonic (G(CD) = -27.4 kcal mol-1) and thus it compensates the
endergonic formation of intermediate B (G(AB) = +15.2 kcal
mol-1 at the first stage of the reaction pathway. Finally, D is
deprotonated by the base, yielding the final product. The whole
process is both thermodynamically (G(AD) = -17.2 kcal mol-1)
and kinetically favorable (the highest transition state TSB-C is only
17.8 kcal mol-1 less stable energetically compared to the sum of the
reactants A). Therefore, the computed mechanism suggests that
the reaction can readily proceed at room temperature, in
accordance with the experimental evidence.
R
O
Cs2CO3 (1.2 equiv.)
CH2Cl2, 16 h, rt
HO
R
+ R4SeI
SR3
R
SR3
R
SeR4
O
Me
O
Et
Me
O
Me
SC8H17
Et
SC8H17
Me
SMe
SeBu
SeBu
61%
SeBu
26
24
72%
25
71%
O
Me
O
Me
O
Me
Me
SBn
O
Me
SMe
78%
Me
SMe
SeBu
78%
Se
SeBn
29
28
74%
27
Finally, as an application, we have performed a derivatization of the
thioester products by a Fukuyama coupling reaction29 with Et2Zn,
smoothly delivering the corresponding ketone in moderate yield
(Scheme 4).
Cl
Me
O
Me
O
Me
Me
Me
Me
SMe
Me
SMe
Me
SC8H17
Se
Se
Se
Me
70%
Cl
Me
O
Me
O
Pd(PPh3)2Cl2 (10 mol%)
Et2Zn, PhMe, r.t.
30
Me
31
32
70%
75%
CF3
Me
Me
SBn
Me
Et
O
O
Me
O
SePh
SePh
5
39
, 57% yield
Me
SC8H17
Me
SMe
SMe
Se
Se
Se
Scheme 4. Derivatization of the product
In summary, we have presented a new methodology for the
synthesis of a broad range of α-selanyl-α,β-unsaturated thioesters
by a Meyer-Schuster-type rearrangement of propargylic thioalkynes
and selenium electrophilic species. The reaction proceeds through
the initial activation of the thioalkyne with a soft selenium
electrophile, leading to a sulfur-stabilized vinyl cation, which
undergoes an intramolecular attack, forming an oxetene
intermediate, which in turn, decomposes to the final product.
Support for the mechanism was obtained from quantum chemical
calculations underlining the kinetic and thermodynamic favored
nature of the process.
Me
Me
71%
35
68%
O
33
34
88%
O
Me
O
Me
Me
Me
SMe
SMe
Me
SMe
Se
S
Se
Ph
38
80%
37
62%
36
65%
Scheme 3. Scope of diselenides
In order to get additional information on the reaction pathway,
quantum chemical calculations have been performed (Figure 1). The
first step AB is the SN2 type attack of phenylselenyl iodide on the
alkyne with the formation of a ketenethionium intermediate B. The
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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Journal Name
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I
SePh
SePh
SMe
PhSe
SMe
O
O
H
H
C
SMe
O
H
I
I
TSB-C
TSA-B
15.9
TSC-D
14.5
B
17.8
C
15.2
10.2
A’
PhSe
SePh
A
4.2
C
SMe
0.0
SMe
O
H
O
H
D
HO
SMe
SMe
-17.2
I
I
+
I
H
O
PhSeI
PhSe
Figure
1.
Computed
relative
free
energy
profile
, kcal
(DLPNO-CCSD(T)/def2-TZVP//B3LYP-D3/def2-SVP, G298,DCM
mol-1) for the conversion of the reactants A (taken as a reference
0.0 kcal mol-1) to the final intermediate D.
We thank CNPq, CAPES, and INCT-Catálise for financial support.
Calculations were partially performed at the Vienna Scientific
Cluster (VSC). Profs. Nuno Maulide and L. González (Univ. Vienna)
are gratefully acknowledged for support and helpful discussions.
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Conflicts of interest
There are no conflicts to declare.
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COMMUNICATION
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DOI: 10.1039/D0CC07019J
Meyer−Schuster-type Rearrangement for the Synthesis of
α-Selanyl-α,β-Unsaturated Thioesters
Lucas L. Baldassari,a Anderson C. Mantovani,a Micaela Jardim,a Boris Maryasin,b,c,* and Diogo S. Lüdtkea,*
a. Instituto de Química, Universidade Federal do Rio Grande do Sul, UFRGS, Av. Bento Gonçalves 9500, 91501-970, Porto Alegre, RS, Brazil.
b. Institute of Organic Chemistry, University of Vienna, WähringerStraße 38, 1090 Vienna, Austria.
c. Institute of Theoretical Chemistry, University of Vienna, WähringerStraße 17, 1090 Vienna, Austria.
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