Chemoselective rearrangement reactions of sulfur ylide derived from diazoquinones and allyl/propargyl sulfides

Article abstract of DOI:10.1021/acs.orglett.0c03493

Here, we describe three types of rearrangement reactions of sulfur ylide derived from diazoquinones and allyl/ propargyl sulfides. With Rh₂(esp)₂ as the catalyst, diazoquinones react with allyl/propargyl sulfides to form a sulfur ylide, which undergoes a chemoselective tautomerization/[2,3]-sigmatropic rearrangement reaction, a Doyle?Kirmse rearrangement/Cope rearrangement cascade reaction, or a Doyle?Kirmse rearrangement/elimination reaction, depending on the substituent of the sulfides. The protocol provides alkenyl and allenyl sulfides and multisubstituted phenols with moderate and high yields.

Full text of DOI:10.1021/acs.orglett.0c03493

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Letter
Chemoselective Rearrangement Reactions of Sulfur Ylide Derived
from Diazoquinones and Allyl/Propargyl Sulfides
Sijia Yan, Junxin Rao, and Cong-Ying Zhou*
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ABSTRACT: Here, we describe three types of rearrangement
reactions of sulfur ylide derived from diazoquinones and allyl/
propargyl sulfides. With Rh2(esp)2 as the catalyst, diazoquinones
react with allyl/propargyl sulfides to form a sulfur ylide, which
undergoes a chemoselective tautomerization/[2,3]-sigmatropic
rearrangement reaction, a Doyle−Kirmse rearrangement/Cope
rearrangement cascade reaction, or a Doyle−Kirmse rearrange-
ment/elimination reaction, depending on the substituent of the
sulfides. The protocol provides alkenyl and allenyl sulfides and
multisubstituted phenols with moderate and high yields.
hereas transition-metal-catalyzed carbene transfer re-
actions of diazo compounds have been well-established
give alkenyl and allenyl sulfides and multisubstituted phenols,
respectively, depending on the sulfide substituents (Scheme
1b). The relative structures of the products have been found in
many bioactive molecules (Scheme 1c).8
W
as powerful tools for C−C and C−heteroatom bond
formation,1 examples of the use of cyclic diazo compounds
as the carbene source are scarce. Diazoquinones are a class of
planar six-membered ring compounds with carbonyl, alkene,
and diazo groups in conjugation.2 The unique structure
endows the quinoid carbene some distinctive reactivity profiles
such as the tendency for aromatization,3−6 high electro-
philicity,3a,e,4e and quinone-like hydrogen atom transfer (HAT)
reactivity.3h,6c In recent years, diazoquinones have attracted
increasing attention as unusual carbocyclic carbene sources and
phenol synthons.3−6 They have been demonstrated to be
reactive for a variety of carbene transfer reactions, including
C−H insertion,3 cyclopropanation,4 and O−H insertion.5
However, compared to that of traditional acyclic diazo
compounds, such as ethyl diazoacetate and methyl phenyl-
diazoacetate, there is currently a rather limited knowledge of
diazoquinones in catalytic carbene transformations.
Transition-metal-catalyzed [2,3]-sigmatropic rearrangement
reactions of diazo compounds and allylic sulfides, namely, the
Doyle−Kirmse reaction, represent a powerful method for the
reorganization of molecular skeletons and C−C bond
formation (Scheme 1a), which has found many applications
in the synthesis of bioactive natural products and pharma-
ceuticals.7 α-Diazoacetates have been demonstrated to be
effective carbene precursors for such reactions. To our
knowledge, there has been no report on rearrangement
reactions of sulfur ylide derived from diazoquinones with
allylic sulfides. In view of the unusual structural and electronic
properties of diazoquinones, new reaction patterns for
diazoquinones and allylic sulfides would be expected. Herein,
we report three types of rearrangement reactions of sulfur ylide
derived from diazoquinones and allyl/propargyl sulfides, which
At the outset, we investigated the reaction between
diazoquinone 1a and allylic sulfide 2a (Table 1). With
Rh2(esp)2 as the catalyst, the reaction proceeded smoothly at
40 °C to give a rearrangement product 3a with a 98% yield
(entry 1), and no Doyle−Kirmse reaction product was
observed. Other dirhodium catalysts, including Rh2(OAc)4,
Rh2(oct)4, Rh2(tpa)4, and Rh2(tfa)4, are less efficient than
Rh2(esp)2, giving 3a in 5−65% yield. Copper complexes,
Cu(acac)2, Cu(MeCN)4BF4, and Cu(hfac)2, which have been
reported to be effective for sulfur ylide transformations with α-
diazoacetates as the carbene source,9 failed to catalyze the
rearrangement reaction under the same conditions. Solvent
screening showed that toluene or CH3CN gave 3a in a yield
comparable to that of ClCH2CH2Cl (DCE), but the use of
tetrahydrofuran (THF) had a detrimental effect on the
reaction, giving 3a in low yield. The rearrangement reaction
was performed in a one-pot fashion without the need for the
slow addition of diazoquinones.
With the optimized condition, the substrate scope of the
reactions was examined. As shown in Scheme 2, a range of
allylic sulfides underwent the rearrangement reaction with
diazoquinone 1a with moderate to high yields. We first
Received: October 20, 2020
https://dx.doi.org/10.1021/acs.orglett.0c03493
© XXXX American Chemical Society
Org. Lett. XXXX, XXX, XXX−XXX
A

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a-c
Scheme 1. Rearrangement Reactions of Sulfur Ylide
Scheme 2. Reaction of Diazoquinones with Allyl Sulfides
a c
−
Table 1. Optimization of Reaction Conditions
entry
catalyst
solvent
temp (°C) time (h) yield (%)
1
2
3
4
5
6
7
8
Rh2(esp)2
Rh2(OAc)4
Rh2(oct)4
Rh2(tpa)4
Rh2(tfa)4
Cu(acac)2
Cu(hfac)2
Cu(MeCN)4BF4
Rh2(esp)2
Rh2(esp)2
Rh2(esp)2
Rh2(esp)2
Rh2(esp)2
Rh2(esp)2
Rh2(esp)2
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
THF
toluene
CH3CN
DCE
40
40
40
40
40
40
40
40
30
50
60
40
40
40
40
20
20
20
20
20
20
20
20
24
13
6
98
46
41
65
5
trace
0
trace
73
97
81
7
90
81
83
9
10
11
12
13
14
a
The reaction was conducted with 0.3 mmol 1 and 0.9 mmol 2 in 2.0
20
20
20
20
b
c
1
mL of DCE. Isolated yield. The dr ratios were determined by H
NMR of the reaction mixture.
c
15
a
The reaction was performed with 0.3 mmol 1a and 0.9 mmol 2a in
rearrangement products with 41−96% yields (3a−3e). Bromo
and phenyl substituents were found to be tolerant to the
reaction, giving the desired product 3f and 3g in 86 and 40%
yields, respectively.
b
1
2.0 mL of solvent under argon. Determined by H NMR analysis of
the reaction mixture using 1,3,5-trimethylbenzene as an internal
standard. 0.45 mmol 2a (1.5 equiv) was used.
c
In addition to linear allylic sulfides, lactone- and cyclic-
ketone-derived allylic sulfides are also reactive in the
rearrangement reaction, giving corresponding products bearing
a quaternary center with good yields (3h, 3i). Benzoxazole is a
common moiety in pharmaceutical compounds and bioactive
investigated the substitution effect of the allyl moiety on the
reaction. Various substitution patterns including β and γ
substitutions, mono- and disubstitutions, and cyclic substitu-
tions are compatible with the reaction, giving corresponding
B
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natural products.10 The benzoxazole-derived allyl sulfide can
undergo the rearrangement reaction to give a benzoxazole-
containing sulfide with a good yield (3j).
silane-substituted propargyl sulfide is reactive, giving allenylsi-
lane 5c in a 94% yield. Allenylsilanes have been demonstrated
to be key intermediates in the synthesis of many complex
natural products.12 In addition to the ester group, the R3
group, such as lactone and amide, is also compatible with the
rearrangement reaction, giving corresponding allenyl sulfides
with good yields (5e, 5f).
The scope of diazoquinones was also examined in the
rearrangement. As shown in Scheme 3, various substituted
diazoquinones are reactive and give desired allenyl sulfides
with moderate to high yields (5g−5l).
The scope of diazoquinones was also examined with sulfide
2a as the substrate. As depicted in Scheme 2, various
diazoquinones, including meta-, ortho-, and disubstituted
diazoquinones, are effective carbene precursors for the
Rh(II)-catalyzed rearrangement reaction, affording good to
high product yield (60−98%, 3k−3p). In the case of 3k, the
moderate product yield might be attributed to the poor
solubility of unsubstituted diazoquinone 1b in 1,2-dichloro-
ethane. Compared to diazoquinone 1a, the reaction with ester-
substituted diazoquinone 1c was slower; this observation is
consistent with the electron-withdrawing group often make
diazo compounds less susceptible toward metal-catalyzed
decomposition.11
We next investigated the reaction of propargyl sulfides with
diazoquinones, which provides efficient access to allenyl
sulfides. As shown in Scheme 3, a variety of propargyl sulfides
reacted with diazoquinone 1a to give the corresponding allenyl
sulfides 5a−5d in high yields. Internal alkynes are well-
tolerated for the reaction, leading to the formation of 1,1-
disubstituted allenyl sulfides (5b−5d). It is worth noting that
We next investigated the substitution (R1) effect of allylic
sulfides on the reaction (Table 2). Interestingly, it is found that
varying substituent R1 could dramatically change the reaction
pathway of the reaction with diazoquinones. When phenyl allyl
sulfide was used, the reaction with diazoquinone 1a gave a
phenylthio-substituted phenol 7a as a major product with a
64% yield and a regioisomeric ratio of 2.6:1, along with phenol
8a as a minor product (entry 1). The toluene substituent led to
a similar result (entry 2). When electron-deficient aryl
substituents were used, the reaction required longer reaction
time and higher temperature to be completed (entries 3−5).
The ratio of 7/8 was around 1:1−3.5 when diazoquinones 1b,
1c, and 1d were used as the carbene precursors (entries 6−8).
However, when R1 is an alkyl group, the reaction of allylic
sulfides with diazoquinone 1a or 1d led to the formation of
only 8a or 8d with good yield, and no product 7 was observed
(entries 9−12).
Scheme 3. Reaction of Diazoquinones with Propargyl
a,b
Sulfides
Product 7 presumably stems from the cascade reaction of
Doyle−Kirmse rearrangement and Cope rearrangement of
sulfur ylide. This hypothesis is supported by the control
experiments in Scheme 4. Treatment of 4-chlorophenyl allyl
sulfide 6c with diazoquinone 1a or 1b at 40 °C for 20 h gave
Doyle−Kirmse reaction products 9 and 10 in 69 and 60%
yields, respectively (Scheme 4a). The structure of 10 was
unambiguously confirmed by X-ray crystallography. The
electron-withdrawing groups on the aryl moiety were found
to stabilize the Doyle−Kirmse reaction product and vice versa
(Table 2, entries 1 and 2 vs entries 3−5). This observation is
reminiscent of the rate acceleration of the anionic oxy-Cope
reaction, where an anionic alkoxy group substantially weakens
the adjacent C(3)−C(4) bond presumably due to anionic
hyperconjugation.13 Compound 9 was observed to convert to
compound 7 with a regioisomeric ratio of 3:1 at 60 °C via
Cope rearrangement (Scheme 4b). It is worth noting that
Rh2(esp)2 could facilitate the Cope rearrangement, as the
conversion of the reaction is low in the absence of Rh2(esp)2
under the same conditions. This result is consistent with the
previous reports that Bronsted and Lewis acids are capable of
promoting Cope rearrangement presumably by delocalization
of the charge and the six electrons of the Cope transition
state.14 Along with 7, phenol 8a and disulfide 11 were also
observed in the control experiment, indicating that the
formation of 8 arose from the elimination of the thio group
from the Doyle−Kirmse reaction product.
A tentative reaction mechanism is proposed in Scheme 5.
Dirhodium carboxylate decomposes diazoquinone to generate
a metallo-quinone carbenoid species which is trapped by the
allylic sulfide to form a free sulfur ylide or metal-associated
sulfur ylide.15 Depending on the R2 substituent of the sulfides,
the sulfur ylide can proceed via three possible pathways. In
path A (R2 = ester), the sulfur ylide undergoes a rapid
tautomerization to give intermediate II due to the acidity of
a
The reaction was conducted with 0.3 mmol 1 and 0.9 mmol 4 in 2.0
b
mL of DCE. Isolated yield.
C
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a c
−
Table 2. Reaction of Diazoquinones with Aryl Allyl Sulfides or Alkyl Allyl Sulfides
yield
entry
1
R1
R2
H
R3
7
8
Ph
Br
Br
Br
Br
Br
H
64%
23%, 8a
(7a′/7a″ = 2.6:1)
2
4-Me-Ph
4-Cl-Ph
4-F-Ph
H
H
H
H
74%
4%, 8a
(7b′/7b″ = 3:1)
c
3
33%
64%, 8a
40%, 8a
48%, 8a
(7c′/7c″= 2:1)
c
4
52%
(7d′/7d″ = 4.1:1)
c
5
4-CF3-Ph
50%
(7e′/7e″ = 1.9:1)
6
7
4-Me-Ph
Ph
H
H
32%, 7f
25%
41%, 8b
21%, 8c
CO2Me
(7g′/7g″ = 8:1)
8
9
10
11
12
Ph
Me
Cl
H
H
H
Cl
H
21%, 7h
75%, 8d
53%, 8a
55%, 8a
60%, 8a
42%, 8d
Br
Br
Br
H
0
0
0
0
CH2CHCH2
CH2Ph
CH2CHCH2
a
b
The reaction was performed with 0.3 mmol 1 and 0.9 mmol 6 in 1.2 mL of DCE under argon. Isolated yield (rr ratios were determined by 1H
c
NMR). Temperature = 50 °C, reaction time = 96 h.
Scheme 4. Control Experiments
Scheme 5. Proposed Reaction Mechanism
the α-C−H proton of thioacetate and the propensity of
aromatization of cyclohexadienone. The intermediate under-
goes [2,3]-sigmatropic rearrangement to give product 3. In
path B (R = aryl), sulfur ylide undergoes the cascade reaction
of Doyle−Kirmse rearrangement and Cope rearrangement to
furnish multisubstituted phenol 7. However, in the case of R =
alkyl (path C), the sulfur ylide tends to undergo Doyle−
D
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Kirmse rearrangement and elimination of the thio moiety,
giving product 8. The actual reason why intermediate IV
undergoes elimination in preference to Cope rearrangement is
not clear at this stage.
In conclusion, three types of rearrangement reactions of
sulfur ylide derived from diazoquinone and allyl/propargyl
sulfides were developed. Dependent on the sulfide substituent,
diazoquinones undergo a chemoselective tautomerization/
[2,3]-sigmatropic rearrangement reaction, a Doyle−Kirmse
rearrangement/Cope rearrangement cascade reaction, or a
Doyle−Kirmse rearrangement/elimination reaction, providing
alkenyl and allenyl sulfides and multisubstituted phenols in
moderate and high yields.
ASSOCIATED CONTENT
* Supporting Information
■
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.0c03493.
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Experimental procedures, characterization of new
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Accession Codes
CCDC 2021262 contains the supplementary crystallographic
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via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
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AUTHOR INFORMATION
Corresponding Author
■
Cong-Ying Zhou − College of Chemistry and Materials Science,
Jinan University, Guangzhou 510632, China; orcid.org/
0000-0002-2235-6070; Email: zhoucy2018@jnu.edu.cn
Authors
Sijia Yan − College of Chemistry and Materials Science, Jinan
University, Guangzhou 510632, China
Junxin Rao − College of Chemistry and Materials Science, Jinan
University, Guangzhou 510632, China
́
4815−4819. (f) Jang, Y.-S.; Wozniak, Ł.; Pedroni, J.; Cramer, N.
Access to P-and Axially Chiral Biaryl Phosphine Oxides by
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Int. Ed. 2018, 57, 12901−12905. (g) Ghosh, B.; Samanta, R. Rh (III)-
Catalyzed straightforward arylation of 8-methyl/formylquinolines
using diazo compounds. Chem. Commun. 2019, 55, 6886−6889.
(h) Wang, H.-X.; Richard, Y.; Wan, Q.; Zhou, C.-Y.; Che, C.-M.
Iridium (III) Catalyzed Intermolecular C(sp3)-H Insertion Reaction
of Quinoid Carbene: A Radical Mechanism. Angew. Chem., Int. Ed.
2020, 59, 1845−1850. (i) Li, X.; Wang, J.; Xie, X.; Dai, W.; Han, X.;
Chen, K.; Liu, H. Ir(III)-Catalyzed direct C−H functionalization of
N-phenylacetamide with a-diazo quinones: a novel strategy for
producing 2-hydroxy-20-amino-1,20 -biaryl scaffolds. Chem. Commun.
2020, 56, 3441−3444.
Complete contact information is available at:
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by Start-up fund of Jinan University
and National Natural Science Foundation of China (NSFC
21472159).
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