Selective [5,5]-Sigmatropic Rearrangement by Assembly of Aryl Sulfoxides with Allyl Nitriles

Article abstract of DOI:10.1002/anie.201900434

Aromatic [5,5]-sigmatropic rearrangement is an appealing protocol for accessing 1,4-substituted arenes. However, such a protocol has not been well utilized in organic synthesis because of the difficulties in the synthesis of the substrates, selectivity issues, and limited substrate scope. Described herein is a new [5,5]-sigmatropic reaction utilizing readily available aryl sulfoxides and allyl nitriles. This reaction features mild reaction conditions, high chemo- and regioselectivity, excellent functional-group compatibility, and broad substrate scope. Computational studies suggest that the success of the reaction can be attributed to the selective electrophilic assembly of the rearrangement precursors, in which a linear -C=C=N- linkage favors [5,5]-sigmatropic rearrangement over the competitive [3,3]-sigmatropic rearrangement.

Full text of DOI:10.1002/anie.201900434

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Accepted Article
Title: Selective [5,5]-Sigmatropic Rearrangement via Electrophilic
Assembly of Aryl Sulfoxides with Allyl Nitriles
Authors: Lei Zhang, Jia-Ni He, Yuchen Liang, Mengjie Hu, Li Shang,
Xin Huang, Lichun Kong, Zhi-Xiang Wang, and Bo Peng
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201900434
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10.1002/anie.201900434
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Selective [5,5]-Sigmatropic Rearrangement via Electrophilic
Assembly of Aryl Sulfoxides with Allyl Nitriles
Lei Zhang,+ Jia-Ni He,+ Yuchen Liang,+ Mengjie, Hu, Li Shang, Xin Huang, Lichun Kong, Zhi-Xiang
Wang,* Bo Peng*
Dedication ((optional))
Abstract: Aromatic [5,5]-sigmatropic rearrangement is an appealing
protocol for accessing 1,4-substituted arenes. However, such a
protocol has not been well utilized in organic synthesis, because it
often suffers from the difficulties in the synthesis of substrates,
selectivity issues, and limited substrate scopes. Herein, we describe
a new [5,5]-sigmatropic reaction by utilizing readily available aryl
sulfoxides and allyl nitriles. This reaction features mild conditions,
high chemo- and regioselectivity, excellent functional group
compatibility and broad substrate scope. Computational studies
suggested that the success of the reaction can be attributed to the
selective electrophilic assembling of rearrangement precursors in
which
a
linear -C=C=N- linkage favors [5,5]-sigmatropic
rearrangement over the competitive [3,3]-sigmatropic rearrangement.
[3,3]-Sigmatropic rearrangement is
a powerful process in
organic synthesis, based on which a number of name reactions
have been developed.1,2 The success of this process can be
mainly attributed to its inherent high chemo- and
regioselectivities.
In
sharp
contrast,
[5,5]-sigmatropic
rearrangement reactions, though also thermally allowed by the
Woodward-Hoffmann rules, have not attracted that much
attentions and were rarely reported.3-5 The Claisen-type
rearrangement of phenyl dienyl ethers to the para-functionalized
phenols is a classic [5,5]-sigmatropic rearrangement reaction
(eq 1, Scheme 1a).3 Although the reaction was well developed
with good para-regioselectivity by Naruta in 1986, it has not
caught much attention,3a probably due to the limited substrate
scope. The benzidine rearrangement represents another
important [5,5]-sigmatropic reaction (eq 2).4 The intriguing
reaction pattern has triggered extraordinary efforts of chemists.
However, in addition to the desired para-benzidine, the reaction
also affords side products such as ortho-benzidine, ortho-
semidine, para-semidine, and diphenyline, thus raising
selectivity issues. The addition of phenol to iminoquinone
acetals could also proceed via [5,5]-sigmatropic rearrangement
to form a remote C-N bond (eq 3).5 In spite of these precedents,
to the best of our knowledge, there have been no reports of the
Scheme 1. Background and this work
protocol that could manipulate [5,5]-sigmatropic rearrangement
with high chemo- and regioselectivities, and broad substrate
scope.
The ortho C-H functionalizations of aryl sulfoxides have
garnered great interests in the past decades.6-12 An array of
functionalities including allyl7, propagyl8, carbonyl7,9, phenolic
aryl10, and cyanoalkyl11 groups were selectively anchored on the
ortho position of aryl sulfoxides with electrophilic activation
protocol by Kita, Procter, Maulide, Yorimitsu, Magnier and others.
It’s worth noting that Yorimitsu and coworkers observed para C-
H arylation products in the development of ortho arylation of aryl
sulfoxides with phenols.10a They have also reported an elegant
protocol for para C-H sulfanylation of aryl sulfoxides using alkyl
aryl sulfides as nuleophile.13 In addition, the groups led by Hyatt
and Shafir respectively reported para C-H benzylation of aryl
iodanes via interrupted “transmetalation” process.14
[*]
L. Zhang, J. He, M. Hu, L. Shang, X. Huang, L. Kong, Prof. B. Peng
Key Laboratory of the Ministry of Education for Advanced Catalysis
Materials, Zhejiang Normal University
Jinhua 321004, China
E-mail: pengbo@zjnu.cn
Y. Liang, Prof. Z. Wang
School of Chemistry and Chemical Engineering, University of the
Chinese Academy of Sciences
Beijing 100049, China
E-mail: zxwang@ucas.ac.cn
These authors contributed equally to this work
Recently, we developed an ortho C-H cyanoalkylation of aryl
sulfoxides
(Scheme
1b).11c
In
this
study,
an
[+]
“assembly/deprotonation” strategy, including Tf2O initiated
electrophilic assembly and DABCO promoted deprotonation,
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Table 1. Hypothesis verification and optimization of reaction conditionsa
entry
T1/t1; T2/t2
base
DABCO
yield(3aa/4aa)b
12%/39%
8%/55%
1
2
3
4
5
6
-30 °C/5 min; -30 °C/5 min
-60 °C/18 h; -60 °C /0.5 h
-60 °C/18 h; -100 °C /0.5 h
-60 °C/18 h; -100 °C/0.5 h
-60 °C/18 h; -100 °C/0.5 h
-60 °C/18 h; -100 °C/0.5 h
DABCO
DABCO
7%/84%
DIPEA
38%/53%
37%/39%
23%/27%
4-methylmorpholine
2,6-dimethylpyridine
[a] Reactions were performed on 0.5 mmol scale. Tf2O was added at -78 °C,
then the mixture was warmed to T1. DABCO (2.0 equiv) and other bases (3.0
equiv) were used. [b] Isolated yield.
was implemented to assemble
intermediate which can readily undergo [3,3]-sigmatropic
rearrangement to give ortho-cyanoalkylated product.
a
ketenimine sulfonium
Encouraged by the success of the strategy, we sought to
achieve para C-H functionalizations of aryl sulfoxides by
assembling a vinyl ketenimine sulfonium intermediate as a
precursor for [5,5]-sigmatropic rearrangement, as illustrated in
Scheme 1c.15
To testify our hypothesis, we first investigated the reaction of
allyl nitrile 2a with diphenyl sulfoxide 1a under the conditions for
our reported ortho-cyanoalkylation of aryl sulfoxides (entry1,
Table 1).11c In line with our expectation, aside from the ortho-
cyanoalkylated product 3aa (12%), we obtained para-alkylated
aryl thioether 4aa as a major product (39%). After optimization of
the reaction conditions, we found that employing relatively lower
temperature and prolonging reaction time (Tf2O, -60 °C , 18 h;
DABCO, -100 °C , 0.5 h) could significantly improve the yield of
4aa from 39% to 84%. It’s worth noting that the choice of base is
critical for the selectivity of the reaction. DABCO proved to be
better than other bases (entries 3-6). However, the influence of
base on the regioselectivity is currently not clear.
To our delight, a wide range of allyl nitriles 2 proved to be
suitable for the reaction as shown in Scheme 2. Varying the
linear alkyl chains on γ-position of nitirles (2b-2f) had no obvious
detriment to the reaction. However, nitrile 2g bearing a larger
substituent (secondary alkyl chain) at γ-position produced a
modest yield of 4ag (43%) with a significant amount of ortho-
cyanoalkylated product 3ag (40%). It should be noted that along
with 4ah, trace amount of ortho-cyanoalkylated products 3ah
could also be observed. However, we failed to obtain this side
product even after great efforts. Remarkably, the reaction could
tolerate a diverse array of functional groups including alkyl/aryl
halides (4al, 4ar, 4as, 4au, 4av and 4az), alkyl pseudohalides
(4ak), esters/carbonates (4am-4az), tertiary amines (4aj),
alkenes (4aq), aryl nitriles (4aw), and nitro groups (4ay). These
functional groups tolerated in the reaction provided a versatile
platform for their further derivatization. Impressively, highly
electrophilic functional groups such as unsaturated ester (4aq)
Scheme 2. Reaction scope. [a] Yields of ortho-functionalized arenes 3 are
given in parentheses. T1 = -60 °C (4aa-4al, 4aa’, 4ab’, 4ja, 4la, 4ma), -
55 °C (4am-4az), -50 °C (4ba-4ia, 4ka, 4na-4pa, 4kj). [b] Nitrile 2 (3.0 equiv)
and DIPEA (2.5 equiv) instead of DABCO were used.
and benzynlic chloride (4as) were also nicely compatible with
the reaction conditions. Nevertheless, allyl nitriles (2a’, 2b’)
bearing β-substituents proved to be unsuitable for the reaction
as the desired products 4aa’ and 4ab’ were obtained in very low
yields (Scheme 2).
Next, we examined a variety of aryl sulfoxides as shown in
Scheme 2 (under dashed line). Reactions of symmetric diaryl
sulfoxides (1b, 1c, 1e-1g) bearing electron-withdrawing groups
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Figure 1. Simplified reaction pathways for the reaction of 1a with 2a. Values in the parentheses are relative free energies (in kcal mol-1).
(Cl, Br, COOMe) proceeded smoothly to afford the para-
cyanoalkylated products (4ba, 4ca, and 4ea-4ga) in good yields,
respectively. In line with our previously reported ortho-
cyanoalkylation of aryl sulfoxides11c, electron-rich diaryl sulfoxide
1d and 1h bearing methyl groups were unsuitable for the
reaction. Only 10 % of 4ha could be obtained from sulfoxide 1h
while no desired product 4da could be determined from 1d.
These results indicated a remarkable electronic effect in the
reaction. Not surprisingly, electron-rich methyl phenyl sulfoxide1i
was also not suitable for the reaction. To our delight, other alkyl
arylsulfoxides including chloromethylated sulfoxide 1j and n-
butyl sulfoxide 1k produced the desired products 4ja and 4ka,
albeit in low yields (23% and 19%, respectively). Interestingly,
changing the base from DBACO to DIPEA could significantly
improve the yields of 4ja and 4ka (72% and 66%, respectively).
However, even employing DIPEA as base, the reaction of 1i still
could not furnish any desired product. We suspect that the
primary alkyl group (Me) of 1i could be more readily
deprotonated by bases after electrophilic activation which
precludes the desired reaction pathway. Furthermore, alkyl aryl
sulfoxides 1n-1p bearing meta substituents (Br, Cl, COOMe)
(69%). Unfortunately, para-substituted aryl sulfoxides 1q and 1r
could merely afford complex mixtures under standard condtions.
To shed light on the reaction mechanism, we performed
density functional theory (DFT) study of the reaction of 1a with
2a (see SI for computational details). Figure 1 describes the
truncated version of the complete reaction pathways detailed in
Figure S1. Proceeding along the black pathway, Tf2O first
activates 1a, generating an ion pair (PhSOTf+OTf-, see Figure
S1), which then interacts with 2a to form a more stable ternary
intermediate IM1. Subsequently, IM1 undergoes CN
nucleophilic attack via TS1, leading to IM2. The alternative
terminal C=CH2 attack via TS1a is 1.9 kcal mol-1 less favorable,
because an alkene group is less nucleophilic than a nitrile group.
In addition, the exposed CN, compared to C=CH2, enables an
electrostatic attraction between S+ and O-Tf (attached to nitrile
carbon) which is absent in TS1a (see Figure S2). To
demonstrate the computational results we carried out in situ
NMR study in the absence of DABCO (SI5.2), which showed the
generation of IM2. After assembling IM2, the base DABCO
promotes an E1cB elimination process via deprotonation
illustrated by TS2, giving
a vinyl ketenimine sulfonium
produced desired products 4na-4pa in synthetically useful yields, intermediate IM3 which can undergo either [5,5]- or [3,3]-
whereas sulfoxides 1l and 1m bearing ortho substituents (Cl and
Br) affording 4la and 4ma, respectively in slightly lower yields. In
addition to 2a, terminal substituted allyl nitriles 2j could also
react with alkyl aryl sulfoxide 1k producing 4kj in a good yield
sigmatropic rearrangement. The transition state (TS3) for [5,5]-
sigmatropic rearrangement is 9.7 kcal mol-1 lower than TS3a for
[3,3]-sigmatropic rearrangement. Comparing the key bond
lengths given in TS3 and TS3a, the strong disfavor of [3,3]-
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unsaturated nitrile group remained intact. Finally, the scalability
of the reaction was also demonstrated by a gram-scale reaction,
which produced more than 10 grams of 4aa with high efficiency
(70% yield).
In summary, we have developed a new [5,5]-sigmatropic
rearrangement reaction by sequentially treating the mixture of
aryl sulfoxides and β,γ-unsaturated nitriles with Tf2O and
DABCO. The reaction exhibits very high chemo- and
regioselectivity, excellent functional group compatibility, and
broad substrate scope, overcoming the problems often
encountered
in
the
conventional
[5,5]-sigmatropic
rearrangement reactions. DFT mechanistic studies unveil that
the exposure and stronger nucleophilicity of CN site of allyl
nitrile, compared to the C=CH2 site, controls the chemoselectivity
and the linear -C=C=N- linkage in the rearrangement precursor
favors the [5,5]-sigmatropic rearrangement over the competitive
[3,3]-sigmatropic rearrangement. The new strategy is expected
to trigger the development of aromatic [5,5]-sigmatropic
rearrangement reactions.
Scheme 3. Elaboration of product 4aa and gram-scale reactions.
Acknowledgements ((optional))
sigmatropic rearrangement can be attributed to the ring strain of
the six-membered ring involving alinear -C=C=N- linkage. Finally,
the resulting IM4 undergoes facile rearomatization, giving 4aa.
The energetics of the black course well explains the
production of 4aa, but the barrier difference (9.7 kcal mol-1)
between TS3a and TS3 is too large to explain 3aa as a minor
product. Thus, we reasoned that the conformations of the
intermediates featuring an eclipsed 2a fragment could play the
role. Indeed, as depicted by the blue pathway, the pathway can
afford 3aa via [3,3]-sigmatropic rearrangement with feasible
energetics. However, the transition state (labeled as TS3a') for
IM3' to undergo [5,5]-sigmatropic rearrangement could not be
located, which we attributed to the bended vinyl ketenimine
B. P. thanks Zhejiang Normal University and the support of
NSFC-21502171. Z.-X. W. acknowledges the support of NSFC-
21573233.
Keywords: [5,5]-sigmatropic rearrangement • para-C-H
functionalization • electrophilic activation • sulfoxide
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chain geometrically unsuitable for such
a rearrangement.
Compared to the course leading to 4aa, the blue pathway is
kinetically less favorable to afford 3aa, in agreement with the
experimental results. Moreover, as indicated by TS4-TS6,
2a'/IM1'/IM2' can easily interconvert with its counterpart
2a/IM1/IM2, but the conversion of IM3 to IM3' is unlikely,
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sigmatropic rearrangement to give 4aa, because the barrier for
the second [3,3]-sigmatropic rearrangement is 13.2 kcal mol-1
higher than that (0.7 kcal mol-1) for the facile rearomatization to
give 3aa (see Figure S1).
The utility of the reaction was exhibited by further elaboration
of product 4aa. As illustrated in Scheme 2, the nitrile group, C=C
bond, and sulfide group in 4aa could be readily converted to
other functional groups by simple hydrolysis, reduction and
oxidation. As a consequence, α,β-unsaturated ester 5, α,β-
unsaturated aldehyde 6, allylic amine 7 were obtained in 88%,
64% and 50% yields, respectively. Hydrogenation of C=C bond
with Pd/C catalyst quantitatively gave γ-arylated alkylnitrile 8.
Reduction of 4aa with Raney Ni afforded γ-phenylated alkylnitrile
9 with cleavage of C-S bond. The ozone oxidation of C=C bond,
followed by simple reduction, afforded β-arylethanol 10 in 74%
yield. Sulfide group could be readily oxidized to give
corresponding sulfoxide 11 and sulfone 12 whereas α,β-
[3]
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Lei Zhang, Jia-Ni He, Yuchen Liang,
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Lichun Kong, Zhi-Xiang Wang,* Bo
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Selective [5,5]-Sigmatropic
Rearrangement via Electrophilic
Assembly of Aryl Sulfoxides with
Allyl Nitriles
A new aromatic [5,5]-sigmatropic rearrangement reaction has been achieved by
simply treating the mixture of aryl sulfoxides and allyl nitriles with Tf2O and DABCO.
The reaction features high chemo- and regioselectivity which can be a great
challenge for conventional [5,5]-sigmatropic rearrangement reactions.
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