Synthesis of Spirocycles via Ni-Catalyzed Intramolecular Coupling of Thioesters and Olefins

Article abstract of DOI:10.1002/chem.202100390

A nickel-catalyzed intramolecular coupling of thioesters and olefins has been developed for the efficient synthesis of spirocycles, a privileged scaffold commonly found in natural products. This transformation is characterized by the simultaneous transfer of both acyl and thiol moieties to the alkene, with the suppression of decarbonylation and β-hydrogen elimination. Initial mechanistic investigations are consistent with an oxidative addition/olefin insertion/reductive elimination mechanism. The incorporated methylene sulfide substituent can undergo a variety of further reactions to increase molecular diversity and complexity. These results demonstrate that thioester derivatives can be used as powerful building blocks for the assembly of complex scaffolds.

Full text of DOI:10.1002/chem.202100390

Communication
doi.org/10.1002/chem.202100390
Chemistry—A European Journal
Synthesis of Spirocycles via Ni-Catalyzed Intramolecular
Coupling of Thioesters and Olefins
Wenfei Liu+,[a] Wenhua Xu+,[a] Juanjuan Wang,[a] Hong Lu,[a] Peng-Fei Xu,[b] and Hao Wei*[a]
Abstract: A nickel-catalyzed intramolecular coupling of
thioesters and olefins has been developed for the efficient
synthesis of spirocycles, a privileged scaffold commonly
found in natural products. This transformation is character-
ized by the simultaneous transfer of both acyl and thiol
moieties to the alkene, with the suppression of decarbon-
ylation and β-hydrogen elimination. Initial mechanistic
investigations are consistent with an oxidative addition/
olefin insertion/reductive elimination mechanism. The in-
corporated methylene sulfide substituent can undergo a
variety of further reactions to increase molecular diversity
and complexity. These results demonstrate that thioester
derivatives can be used as powerful building blocks for the
assembly of complex scaffolds.
Figure 1. Representative natural products containing spirocyclic scaffolds
tethered allyl fragment.[4] Recently, the Newman group ex-
panded the scope of this methodology to include aromatic
esters (Figure 2A).[5]
Spirocycles are valuable skeletons that are ubiquitous in natural
products and widely used in the preparation of catalysts,
ligands, agrochemicals, and pharmaceuticals (Figure 1).[1] Spiro-
cyclic scaffolds present unique advantages in drug develop-
ment, because their dense and rigid structures can reduce the
conformational entropy penalty resulting from binding to a
target protein in a favorable geometry.[2] In light of this, there is
a fundamental need to develop efficient methods to access
these compounds from readily available precursors.
In recent years, carboxylic acid derivatives have shown
potential as alternatives to conventionally used organohalides
in transition-metal-catalyzed cross-coupling reactions.[3] The use
of carboxylic acid derivatives as coupling partners offers several
advantages such as low-cost, ease of handling, facile prepara-
tion and the absence of halogenated waste. In 2017, Garg and
Stanley independently reported intramolecular cyclization via
the intramolecular coupling of an aromatic amide and a
Inspired by these seminal works, we propose that valuable
spirocyclic skeletons could be formed by intramolecular
coupling between a carboxylic acid derivative and an olefin. To
prevent wastage of the remaining heteroatom fragment, a
more constructive process entails cleavage of the C(=O)À Z
single bond and addition both fragments across an olefin,
thereby enabling the simultaneous formation of new CÀ C and
CÀ Z bonds (Figure 2B).[6] However, the use of aliphatic carbox-
ylic acid derivatives for the synthesis of spirocyclic skeletons via
this strategy remains formidably challenging because of two
major side reactions: 1) the coupling of aliphatic carboxylic acid
derivatives is exacerbated due to competing decarbonylative
elimination,[7] which is rapid and efficient when transition-metal
catalysts are employed. Thus, if olefin insertion is slow,
decarbonylative product formation will dominate;[8] 2) common
alkyl-metal intermediates tend to undergo β-hydride elimina-
tion side reactions rather than the desired CÀ Z bond
formation.[9]
Sulfur-containing compounds often possess various bio-
logical activities and serve important functions in the pharma-
ceutical industry.[10] Approximately 20% of all FDA-approved
drugs are organosulfur compounds.[10c] Thioesters are more
reactive than the analogous oxoesters and amides due to the
poorer orbital overlap between the sulfur atom and the
carbonyl group.[11] It was expected that the oxidative addition
of a transition metal into the CÀ S bond of thioesters would
proceed under relatively mild conditions,[12] thus preventing the
competing decarbonylation.[13] Consequently, a “cut and sew”
sequence between a thioester and an olefin can be envisaged
to proceed via olefin migratory insertion and reductive
[a] W. Liu,+ Dr. W. Xu,+ J. Wang, Dr. H. Lu, Prof. Dr. H. Wei
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry
of Education, College of Chemistry & Materials Science
Northwest University
Xi’an 710069 (P. R. China)
E-mail: 20154894@nwu.edu.cn
[b] Prof. Dr. P.-F. Xu
Key Laboratory of Applied Organic Chemistry College of Chemistry and
Chemical Engineering, Lanzhou University
Lanzhou 730000 (P. R. China)
[+] These authors contributed equally to this work.
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/chem.202100390
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Table 1. Screening of reaction conditions.[a]
Entry
Ligand
Additive
Yield[b] [%]
1
2
3
4
L1 (DPPE)
L2 (DPPPr)
L3 (DPPB)
L4 (DPPPent)
–
–
–
–
<5
<5
40
28
0
5
L5
–
6
7
L6
L7
–
–
<5
0
8
9
L8
L9
–
–
–
–
49
46
<5
<5
68
64
73
82
0
10
11
12
13
14
15
16[c]
17
L10
L11
L12
L12
L12
L12
L12
–
–
4-CF3-Py
DMAP
4-Piperidino-Py
4-Piperidino-Py
4-Piperidino-Py
0
[a] Reactions conditions: 1a (0.2 mmol), Ni(cod)2 (0.02 mmol,), ligand
°
(0.04 mmol) and additive (0.04 mmol) in THF/H2O (1:1) at 120 C for 24 h.
[b] Isolated yields. [c] Without Ni(cod)2.
Figure 2. Intramolecular coupling between carboxylic acid derivatives and
olefins.
substituents on the phosphorus atom, were tested (entries 5–
12). The results indicated that L12 improved the yield of 2a to
68%, but unreacted 1a (19% yield) still remained under these
reaction conditions (entry 12). This outcome was likely due to
the low reactivity of 1a. We envisaged that modulation of the
steric and electronic properties of the nickel center through
ligand variation would accelerate the nickel-mediated catalytic
cycle and further improve the yield of 2a.[16] Accordingly, we
examined pyridine derivatives bearing a range of substituents
at the para position with different electronic properties (entries
13–15). These derivatives had a beneficial effect on the reaction,
and electron-rich DMAP afforded a higher yield of 2a (73%),
compared to that obtained with electron-deficient 4-CF3Py
(64%). To our delight, a highest yield (82%) was produced with
the 4-piperidinopyridine (20 mol%) as a co-ligand (entry 15).
Finally, the absence of either the nickel catalyst or ligand
resulted in no product (entries 16 and 17), thus demonstrating
that Ni(cod)2/L12 plays an essential role in promoting the
catalytic cycle.
elimination, then enabling the rapid synthesis of spirocyclic
scaffolds. A pendant methylene sulfide substituent on the
spirocyclic skeleton is a suitable handle for further reactions,
enabling increase in molecular diversity and complexity.[14]
Despite advances entailing the use of alkynes[12a,b] and
norbornenes[12e] as coupling partners, to the best of our
knowledge, thioacylation of simple alkenes with thioesters has
no precedent in the literature. Herein, we describe the develop-
ment of Ni-catalyzed intramolecular coupling between thioest-
ers and alkenes for the construction of spirocycles (Figure 2C).
In addition to a modular access to diverse spirocycles, this work
is further highlighted by the potential value of sulfur-containing
molecules in drug discovery and organic synthesis.
For our initial investigation of the proposed cyclization,
readily accessible thioester 1a was used as the model substrate
(Table 1). This substrate could be constructed in two steps from
commercially available cyclohexanecarboxylic acid. It is known
that bidentate ligands can facilitate migratory insertion and
reductive elimination.[15] Various bidentate phosphine ligands
with different bite angles were subjected to the catalytic
transformation (entries 1–4) and the results indicated that DPPB
was the most efficient (entry 3). Furthermore, variants of DPPB,
including analogs bearing more rigid ligands and a range of
With the optimized conditions in hand, we next evaluated
the scope of this reaction; the results are shown in Table 2.
Gratifyingly, the reaction exhibited a broad substrate scope.
Thioesters with cyclohexyl, cyclopent(en)yl, cycloheptyl or
cyclododecyl rings were transformed to the corresponding
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Table 2. Substrate scope.[a,b]
°
[a] Reaction conditions: 1 or 3 (0.2 mmol), Ni(cod)2 (0.02 mmol), L12 (0.04 mmol), 4-piperidinopyridine (0.04 mmol) in THF/H2O (1:1) at 120 C for 24 h.
[b] Isolated yields. [c] DPPB (20 mol%) was used as the ligand. [d] dr=1.5:1.
spiro[5.4]decane 2a, spiro[4.4]nonanes 2b and 2c, spiro[6.4]
undecane 2d, spiro[7.4]dodecane 2e, and spiro[11.4]
hexadecane 2f in good yields. Importantly, the reaction
presented an excellent chemoselectivity profile, as fluorides
(2g), ketones (2h), alkenes (2i), ether (2k), and heterocycles
(2l) were well tolerated under the reaction conditions. Poly-
cyclic thioester products, including spiro (2m), fused (2p) and
bridged (2q and 2r) cycles, afforded the corresponding spiro-
cycles in good yields (2ml–2r). When the number of methylene
carbon atoms in the tether between the ring and the alkene
increased, the reaction still proceeded, although the product
yield was diminished (2s). The structures of 2ha and 2n were
confirmed by X-ray diffraction analysis of their single crystals.
Furthermore, several molecules derived from complex natural
products were successfully cyclized using our developed
method. Thus, the transformation of dehydroepiandrosterone,
cholesterol and estrone derivatives gave spirocycle products 2t,
2u and 2v in moderate yields, respectively. Finally, the
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Scheme 1. Mechanistic studies.
reactions of thioesters substituted with an electron-donating or
withdrawing aromatic ring or a naphthyl group produced the
corresponding spiro[5.4]decanes 4a–4j in moderate to good
yields.
In order to further probe the mechanism of this trans-
formation, DFT calculations were performed; the two possible
mechanistic pathways are shown in Figure 3. In path a, olefin
insertion into the NiÀ H bond converts INT3 to INT2 (via TS3),
followed by CÀ S reductive elimination (via TS4), to give the
product. An alternative path is olefin insertion into the NiÀ S
bond (path b), and subsequent CÀ H reductive elimination via
TS6 to form the product. The reductive elimination processes
have the highest energy barriers (TS4 and TS6) in the paths a
and b, respectively. TS4 is more stable than TS6 by 7.3 kcal/mol,
indicating that CÀ S reductive elimination (path a) is preferred.
To demonstrate the practicability of this method, gram-scale
reactions were performed. Thus, the desired product 2a was
isolated in 62% yield on a 1 g scale (Scheme 2). The synthetic
To gain mechanistic insights, several experiments were
performed (Scheme 1). First, the reaction of a mixture of two
different thioesters, 1l and 3f, via the standard conditions led
to the formation of crossover products 4fl and 2a, and
intramolecular cyclization products 2l and 4f (Scheme 1A).
When the reaction of 1p and exocyclic enone 5a was
conducted, 6a was also isolated in 26% yield along with 2p
(40%) (Scheme 1B). Additionally, when dienes 5b was added
under the standard conditions, sulfide 6b were also isolated in
17% yield (Scheme 1C). There results can be rationalized by a
process involving β-hydrogen elimination and reinsertion.
Subsequently, when enone 5p and thiol 7 were subjected to
the standard conditions, the desired product 2p was isolated in
high yield. However, in the absence of the Ni catalyst, 2p was
not observed (Scheme 1D). These observations likewise support
the hypothesis that the CÀ S bond is formed via NiÀ H
insertion.[18]
Based on the above experiments, a plausible mechanism is
proposed, as depicted in Scheme 1D. First, oxidative addition of
the acyl CÀ S bond of thioester produces acyl Ni(II)-intermediate
INT1. Migratory insertion of the tethered alkene to the CÀ Ni
bond leads to intermediate INT2, followed by β-hydride
elimination to give NiÀ H intermediate INT3. At this stage, two
pathways are possible: 1) insertion of the NiÀ H bond into the
olefin, followed by CÀ S reductive elimination to form the
product (path a); 2) olefin insertion into the NiÀ S bond,
followed by CÀ H reductive elimination (path b).
Figure 3. Density functional theory (DFT) calculations for paths a and b.
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Acknowledgements
We are grateful to financial support from the National Natural
Science Foundation of China (NSFC 21971205 and 21632003)
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Conflict of Interest
The authors declare no conflict of interest.
Keywords: addition reaction · cut-and-sew reactions · nickel ·
spiro compound · thioesters
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Manuscript received: February 1, 2021
Version of record online: ■■■, ■■■■
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COMMUNICATION
W. Liu, Dr. W. Xu, J. Wang, Dr. H. Lu,
Prof. Dr. P.-F. Xu, Prof. Dr. H. Wei*
1 – 7
Synthesis of Spirocycles via Ni-
Catalyzed Intramolecular Coupling
of Thioesters and Olefins
A nickel-catalyzed intramolecular
coupling of thioesters and olefins is
reported, which provides unique and
atom-economic access to spirocyclic
scaffolds. This transformation is char-
acterized by the simultaneous transfer
of both acyl and thiol moieties to the
alkene, with the suppression of decar-
bonylation and β-hydrogen elimina-
tion.