Rhenium-Catalyzed Arylation–Acyl Cyclization between Enol Lactones and Organomagnesium Halides: Facile Synthesis of Indenones

Article abstract of DOI:10.1002/anie.202103465

A set of rhenium-catalyzed arylation–acyl cyclizations between (hetero)arylmagnesium halides and enol lactones through a cascade C(sp²)?C(sp²)/C(sp²)?C(sp²) bond formation under mild reaction conditions has been developed. Indeed, a wide range of functional groups on both organomagnesium halides and enol lactones is well tolerated by the simple rhenium catalysis, thus furnishing polyfunctionalized indenones in one-pot fashion and with complete control of the regioselectivity. Moreover, this approach also provides a straightforward synthetic route to neolignan and (iso)pauciflorol F. Mechanistic studies demonstrated that the reaction involves a sequence of syn-carborhenation and intramolecular nucleophilic addition.

Full text of DOI:10.1002/anie.202103465

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Accepted Article
Title: Rhenium-Catalyzed Aryl-Acylcyclization between Enol Lactones
and Organomagnesium Halides: Facile Synthesis of Indenones
Authors: Binjing Hu, Xinyi Cheng, Ying Hu, Xingchen Liu, Konstantin
Karaghiosoff, and Jie Li
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10.1002/anie.202103465
Angewandte Chemie International Edition
RESEARCH ARTICLE
Rhenium-Catalyzed Aryl-Acylcyclization between Enol Lactones
and Organomagnesium Halides: Facile Synthesis of Indenones
Binjing Hu,‡[a] Xinyi Cheng,‡[a] Ying Hu,[a] Xingchen Liu,[a] Konstantin Karaghiosoff,[b] and Jie Li*[a]
[a]
Bining Hu, Xinyi Cheng, Ying Hu, Xingchen Liu, Prof. Dr. Jie Li*
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University
Ren-Ai Road 199, 215123 Suzhou, P. R. China
E-mail: jjackli@suda.edu.cn
[b]
Prof. Dr. Konstantin Karaghiosoff
Department Chemie, Ludwig-Maximilians-Universitat Munchen, Butenandtstr. 5-13, Haus F, 81377 Munich, Germany.
B.H., and X.C. contributed equally.
‡
Supporting information for this article is given via a link at the end of the document.
Abstract: A set of rhenium-catalyzed aryl-acylcyclization between
(hetero)arylmagnesium halides and enol lactones through a cascade
Csp2‒Csp2/Csp2‒Csp2 bond formation has been developed under
mild reaction conditions. Indeed, a wide range of functional groups on
both organomagnesium halides and enol lactones are well tolerated
by the simple rhenium catalysis, thus furnishing polyfunctionalized
indenones in one-pot fashion and with complete control of the
alkynes or alkenes.[14] Hence, we became intrigued by developing
transition metal-catalyzed cross-coupling between enol
lactones and organometallic reagents.
a
regioselectivity. Moreover, this approach also provides
a
straightforward synthesis to neo-lignan and (iso)pauciflorol F.
Mechanistic studies demonstrated that the reaction involves a
sequential of syn-carborhenation and intramolecular nucleophilic
addition process.
Introduction
Rhenium is a 7 group, six-row transition metal, which possesses
versatile reactivity due to its hard and soft Lewis acidity.[1] Since
Figure 1. Indenone or indanone-containing natural products and bioactive
compounds.
2000, rhenium complexes have witnessed significant progress in
2]
cyclization reactions, nucleophilic additions,[1,
as well as
challenging inert C‒H and C‒C bonds functionalizations, [1, 3] thus
providing powerful tools for the construction of unique carbon-
carbon bonds. However, rhenium-catalyzed cross-coupling with
organometallic reagents was rather rare. Organometallics, such
as organomagnesium and organozinc reagents, displayed
excellent functional groups compatibility and versatile reactivity in
transition metal-catalyzed cross-coupling reactions under mild
reaction conditions.[4] Generally, most of these advances were
achieved with the using of unsaturated halides as the
electrophiles. The more environmentally friendly phenol or enol
derivatives (halide-free), such as unsaturated pivalates or
acetates, have obtained considerable recent attentions and been
utilized for transition metal-catalyzed cross-couplings with
organometallic reagents using Pd, Rh, Ni, Co, Fe and Cr catalysis,
as were reported by Shi,[5] Garg,[6] Fꢀrstner,[7] Ackermann,[8] von
Wangelin,[9] Martin,[10] Knochel,[11] and others,[12] thus achieving
novel C‒C bonds formation in a better mass efficiency fashion
(Scheme 1a). However, using enol lactones as the coupling
electrophiles for cross-coupling with organometallic nucleophiles
has unfortunately thus far proven elusive. In particularly, enol
lactones can be easily prepared from ubiquitous phthalic
anhydrides with Witting reagents[13] and benzoic acids with
On the other hand, indenones and their indanone derivatives
are key important structural motifs for material science
applications,[15] as well as of various active natural products and
pharmaceuticals with activities of relevance to biology or
medicinal chemistry,[16] as found in voltage-gated potassium
channel inhibitors against type II diabetes,[17] and peroxisome
proliferator-activated receptor γ (PPARγ) agonists (Figure 1).[18]
Therefore, there is a continued strong demand for developing
efficient and selective synthetic approaches to access these
valuable scaffolds. Traditional synthetic methods lack of
generality and have limited substrate scope.[19] In recent years,
transition metal-catalyzed cyclization with internal alkynes
through chelation-assisted C‒H activation[20] or multiple cross-
couplings[21] has been recognized as an increasingly viable tool
for the preparation of indenones (Scheme 1b). Despite these
major advances made, the poor regioselectivity using
unsymmetrical alkynes as the coupling partners still represent
drawbacks. In this context, Dong and coworkers recently reported
a palladium/norbornene-catalyzed direct Catellani annulation
between unsaturated carboxylic acid anhydrides and aryl iodides,
which realized various indenones synthesis with good
regioselectivity (Scheme 1b).[22].We herein report
a aryl-
1
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10.1002/anie.202103465
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RESEARCH ARTICLE
acylcyclization between various organomagnesium halides and
readily accessible enol lactones through a rhenium-catalyzed
sequential of syn-carbometalation and nucleophilic addition
process, which provides a straightforward approach to the
synthesis of polyfunctionalized indenones in a complete control of
regioselective fashion (Scheme 1c).
9
Co(acac)2 instead of ReCl3
26
16
10
11
12
13
FeCl3 instead of ReCl3
Mn(acac)3 instead of ReCl3
CuCl2 instead of ReCl3
--
37
trace
trace
[a] Reaction conditions: 1a (0.45 mmol, 1.5 equiv), 2a (0.3 mmol, 1.0 equiv),
ReCl3 (5 mol %), THF (1.0 mL), 23 °C, 16 h. [b] Isolated yields. [c] under 0 °C.
We initiated our studies by optimizing reaction conditions for the
envisioned rhenium-catalyzed aryl-acylcyclization between
phenylmagnesium chloride (6a) and (E)-enol lactone (7a). A
cascade cross-coupling reaction was observed in the presence of
5.0 mol % ReCl3 under room temperature, thus delivering the
desired arylated indeone 8 in 78% yield (Table 1, entry 1). A
number of representative chelating ligands, such as bipyridine
(L1), tridentate 2,6-bis(N-pyrazolyl)pyridine (L2), N-heterocyclic
carbene (L3) and TMEDA (L4), gave significantly decreased
yields (entries 2‒5). Switching from ReCl3 to other representative
transition-metals, such as CoCl2, Co(acac)3, FeCl2, FeCl3, MnCl2,
Mn(acac)3, CuCl2, or in the absence of metal catalyst, led to poor
yields of the desired product of 8 (entry 6‒13).
Scheme 1. a) cross-couplings with unsaturated carboxylates, b) Indenone
synthesis
and
c)
rhenium-catalyzed
aryl-acylcyclization
between
organomagnesium halides and enol lactones.
Results and Discussion
Table 1. Optimization for rhenium-catalyzed arylation/acylcyclization.[a]
Scheme 2. Scope of arylmagnesium reagents for rhenium-catalyzed
aryl/acylcyclization domino reaction.
Entry
Modified conditions
Yield (%)[b]
Having identified optimized rhenium catalysis in hand, we
subsequently explored the substrate scope of various
arylmagnesium reagents for the rhenium-catalyzed cascade
cross-coupling reaction with (E)-enol lactones (7a‒7b) (Scheme
2). A range of arylmagnesium reagents bearing various valuable
electrophilic functional groups, such as methyloxyl, trimethylsilyl,
dimethylamino, acetal, trifluoromethyl, (tert-butyldimethylsilyl)oxyl,
fluoro, chloro, methylenedioxyl, difluoromethylene dioxyl
substituents, as well as methyloxylnaphthyl magnesium bromide
underwent the aryl-acylcyclization with 7a or 7b to afford the
1
3
3
4
5
6
7
8
None
78 (75)[c]
L1 (6 mol %) was used as a ligand
L2 (6 mol %) was used as a ligand
L3 (6 mol %) was used as a ligand
L4 (6 mol %) was used as a ligand
CoCl2 instead of ReCl3
22
35
38
36
7
FeCl2 instead of ReCl3
14
28
MnCl2 instead of ReCl3
2
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10.1002/anie.202103465
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RESEARCH ARTICLE
desired products 9‒19 in 54‒97% yields. More sterically hindered
ortho-substituted aryl Grignard reagents were successfully
employed as nucleophiles for the envisioned cascade cross-
couplings, thereby providing the corresponding products 20‒21 in
good yields. The arylmagnesium bromides bearing fluoro and
chloro substituents were identified to be suitable as well, albeit
only delivering the indenones 22‒23 in modest yields. It is
thus leading to the 2,3-unsymmetric diarylated or arylalkylated
indenones 34‒38 in 39‒78% yields with complete control of
regioselectivity. Notably, both Larock annulation[16a] and C‒H
activation[20] strategies with unsymmetric internal alkynes remain
challenges of the regioselectivity. The late-stage derivatization of
the obtained indenone 38 was demonstrated by a subsequent
direct ruthenium-catalyzed C‒H arylation process.[23]
noteworthy that
smoothly with (E)-alkenyl lactone 7a, giving the ferrocenylated
product 24 in 59% yield.
a
ferrocenyl magnesium bromide reacted
Cross-couplings with heterocyclic moieties are of special
important in pharmaceutical and agrochemical research.[24]
Importantly, this rhenium catalysis is not limited to the aromatic
Grignard reagents. Indeed, our rhenium catalyst showed
comparable levels of catalytic efficacy for the described cascade
cross-coupling reactions between various heteroarylmagnesium
halides and alkenyl carboxylates, thus yielding the thiophene-,
pyrimidine-, (di)benzothiophene-, indole- and pyridine-based
indenones 40‒47 in moderate to high yields (Scheme 4). Among
them, the structure of 43 was confirmed by X-ray crystal
analysis.[25]
Scheme 4. Substrate ccope of heteroarylmagnesium reagents leading to
indenones. [a] Under 23 °C, 16 h.
Scheme 3. Rhenium-catalyzed cascade cross-coupling reaction with
unsaturated carboxylates of type 7. [a] Under 50 °C, 16 h. [b] 5.0 mmol scale.
[c] 1-phenyl-1H-pyrazole (0.24 mmol), 38 (0.2 mmol), Ru(MesCO2)2(p-cymene)
(5.0 mmol %), K2CO3 (2.0 equiv), PhMe, 120 °C, 20 h.
Subsequently, the versatility of this optimized rhenium catalyst
was examined in a range of aryl-acylcyclization reactions with
various alkenyl lactones 7 and polyfunctionalized arylmagnesium
halides 6 (Scheme 3). As shown, a number of alkenyl lactones
bearing methyl, tert-butyl, methyloxyl, chloro, bromo, naphthyl
groups on the aryl moiety could be successfully employed as
coupling partners in this cascade coupling reaction, providing the
desired products 25‒33 in 37‒82% yields. Moreover, aryl or alkyl
substituted on the alkenyl moiety of the lactones also proved to
be viable substrates for the rhenium-catalyzed aryl-acylcyclization,
3
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Scheme 6. Control experiments.
Intrigued by the remarkable efficacy of this simple rhenium-
catalyzed aryl-acylcyclization, a series of preliminarily control
experiments were performed (Scheme 6). Firstly, we performed
experiments of ReCl3 (1.0 equiv) with excess of p-tolylmagnesium
chloride under typical reaction conditions for 3 h, which generated
the homocoupling product 52 in near 0.66 equiv ratio to that of
ReCl3. These findings might suggest the formation of low-valent
of Re-species under the standard reaction conditions (scheme
6a). Furthermore, the well-defined rhenium(I) species of
ReCl(CO)5 was examined as the catalyst for the envisioned cross-
coupling between PhMgCl (6a) and enol lactone (7n). However,
the desired indenone 37 was only delivered in 32% yield (Scheme
6b). An in situ formed low-valent rhenium-species reduced by
stoichiometric p-ClC6H4MgBr could further promote the cross-
coupling between PhMgCl (6a) and 7n, thus leading the indenone
37 in 53% yield (Scheme 6c). In order to unravel the catalysts
working mode, a carbonyl alcohol 53 (24%) was obtained when
performing the reaction at 23 °C (Scheme 6d). This isolated
intermediate was then subjected to the catalytic reaction
conditions to lead smoothly to the dehydrated indenone 37 in 46%
yield. Importantly, dehydration did not occur in the absence of
arylmagnesium halide (Scheme 6e). These results demonstrated
the cascade aryl-acylcyclization process involved in a sequential
of carbometalation and nucleophilic addition process.
Scheme 5. Rhenium-catalyzed arylation/acylcyclization/Diels-Alder reaction
with (Z)-enol lactone of type of 48.
Additionally, we were also pleased to observe that (Z)-alkenyl
lactone of 48 proved suitable to generate the highly sensitive
cyclopentadienone, which subsequently occurred Diels-Alder
reaction with another cyclopentadienone under the standard
reaction conditions. The corresponding dimers 49‒51 were
obtained in 44‒68% yields and the structure of 49 was confirmed
by X-ray crystal analysis.[25] In sharp contrast, product 49 was only
formed in a poor yield when employing a (E)-alkenyl lactone of 48
as the coupling partner (Scheme 5).
Scheme 7. Plausible catalytic cycle.
4
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10.1002/anie.202103465
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RESEARCH ARTICLE
In summary, a simple rhenium-catalyzed aryl-acylcyclization
between (hetero)arylmagnesium halides and readily accessible
enol lactones has been developed, which provides a simple and
expedient route to the synthesis of versatile indenones. This
approach proceeds under mild reaction conditions with high
efficacy, displays excellent functional group tolerance, features a
broad substrate scope of (hetero)arylmagnesium reagents, as
well as enol lactones. Mechanistic studies support a in situ formed
Re-species enable a sequential of syn-carborhenation and
intramolecular nucleophilic addition process. Moreover,
straightforward synthesis of neo-lignan and (iso)pauciflorol F
shows the potential applications of this protocol for the discovery
of novel bioactive molecules.
Acknowledgements
We thank the National Natural Science Foundation of China
(Grant No. 21602083) and Start Funding of Soochow University
(Grant No. Q410900520) for financial support.
Keywords: rhenium catalysis • indenone synthesis • aryl-
acylcyclization • enol lactones • organomagnesium halides
Scheme 8. Formal synthesis of neo-lignan, (iso)pauciflorol F through rhenium-
catalyzed aryl-acylcyclization. [a] Reaction conditions: ReCl3 (5 mol %), (Z)-enol
lactones (0.3 mmol), arylmagnesium halides (1.5 equiv), THF (1.0 mL), 50 °C,
16 h.
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derivatives.
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(iso)pauciflorol F (2‒3). In this context, (E)-enol lactones 7o‒7q
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of (E)-enol lactones (7o‒7q) with arylmagnesium bromides, thus
leading to the neo-lignan 1 and the corresponding indenones 58‒
59 in 61‒67% yields (Scheme 8). Notably, indenones 58‒59 can
be readily transferred to (iso)pauciflorol F (2‒3), as was reported
by Jeffery and Sarpong.[16a] These results show the potential utility
of this protocol in medicinal chemistry.
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RESEARCH ARTICLE
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10.1002/anie.202103465
Angewandte Chemie International Edition
RESEARCH ARTICLE
Rhenium-catalyzed aryl-acylcyclization. A range of functionalized organomagnesium halides and enol lactones underwent rhenium-
catalyzed sequential aryl-acylcyclization under remarkably mild reaction conditions, thus providing an expedient route to
polyfunctionalized indenones with complete control of regioselectivity. This approach features its broad substrate scope, excellent
functional group tolerance, and synthetic utility in the straightforward synthesis of biologically relevant molecules.
7
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