Synthesis and Application of Heterocyclic Germatranes via Rhodium-Catalyzed Directed C?H Activation/Annulation with Alkynyl Germatranes and Palladium-Catalyzed Cross-Coupling

Article abstract of DOI:10.1002/adsc.201901633

Rhodium-catalyzed C?H activation and annulation with alkynyl germatranes for the synthesis of heterocyclic germatranes is described. Various heterocyclic germatranes were constructed by this protocol and applied in multiple derivatizations such as palladi

Full text of DOI:10.1002/adsc.201901633

Title: Synthesis and Application of Heterocyclic Germatranes via
Rhodium-Catalyzed Directed C-H Activation/Annulation with
Alkynyl Germatranes and Palladium-Catalyzed Cross-Coupling
Authors: Meng-Yu Xu, Chao Wang, Wei-Tao Jiang, and Bin Xiao
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201901633
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10.1002/adsc.201901633
Advanced Synthesis & Catalysis
UPDATE
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Synthesis and Application of Heterocyclic Germatranes via
Rhodium-Catalyzed Directed C-H Activation/Annulation with
Alkynyl Germatranes and Palladium-Catalyzed Cross-Coupling
Meng-Yu Xu,a Chao Wang,a Wei-Tao Jiang,a and Bin Xiao*a
a
Department of Chemistry, University of Science and Technology of China, Hefei 230026, China. E-mail:
binxiao@ustc.edu.cn.
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
C-H activation[9-15] has been used extensively to
Abstract. Rhodium-catalyzed C-H activation and
annulation with alkynyl germatranes for the synthesis of
heterocyclic germatranes is described. Various
heterocyclic germatranes were constructed by this
protocol and applied in multiple derivatizations such as
palladium-catalyzed cross-coupling reactions.
construct various heterocyclic compounds[10-15], such
as isoquinolones,[10,11] indoles,[12] isoquinolines,[13]
pyridones[10g,14] and pyrroles.[12c,15] Inspired by
Glorius’ previous work[10] (Scheme 1b), we assumed
that Rh(III)-catalyzed C-H activation and following
annulation with pre-prepared alkynyl-Ge could be a
feasible strategy for synthesis of Ge-containing
heterocyclic nucleophiles. Herein, we report the
synthesis of Ge-containing heterocycles via Rh(III)-
catalyzed C-H activation and annulation with
alkynyl-Ge using an internal oxidant (Scheme 1c).
Resulting products could be further used as coupling
partners for Pd-catalyzed cross-coupling reaction
with aryl halides.
Keywords: Rhodium; C-H activation; Annulation;
Alkynyl germatranes; Heterocyclic nucleophiles
Heterocyclic compounds are ubiquitously found in
natural products and biologically active molecules,[1]
which makes the synthesis of heterocycles a
significant task for chemists.[2] The strategy of
constructing stable heterocyclic nucleophilic reagents
containing boron,[3] silion,[4] and tin[5] provides a
powerful tool for further modification. And cross-
coupling reactions of these heterocyclic nucleophiles
have especially enriched the content of heterocyclic
compounds and their derivatives. However, compared
with
other
metal-
or
metalloid-containing
heterocyclic nucleophilic reagents, rather less
attention has been paid to Ge-containing heterocyclic
nucleophiles, since Ge-related cross-coupling
reactions were scarcely reported.[6] Our group has
been focusing on developing a series of facilely
synthesized,
air-
and
moisture-stable
and
environmental-friendly germatranes (abbreviated as
Ge in following text) as nucleophiles for Pd-catalyzed
cross-coupling reaction.[7] Our previous studies have
revealed that germatranization of heterocyclic halides
could furnish various Ge-containing heterocyclic
nucleophiles (Scheme 1a),[7a] which were also proved
to be competent for construction of complex
heterocycles under Pd-catalyzed cross-coupling
reaction conditions. In the light of that, we attempted
to explore a new strategy for the construction of Ge-
containing heterocyclic nucleophiles.
Scheme 1. Construction of Heterocyclic Nucleophilic
Reagents.
To establish practical method for the synthesis of
diversified alkynyl-Ge, the reaction of alkynyl
Grignard reagents with Ge-Cl[7a] (a specie derived
from inexpensive industrial GeO2) was performed.
However, it turned out to be facile but non-ideal due
to the limited commercial source of alkynyl Grignard
reagents. In fact, only ethynyl-Ge was synthesized by
For the last decades, transition metal-catalyzed C-
H activation,[8] especially Rh(III)-catalyzed directed
1
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10.1002/adsc.201901633
Advanced Synthesis & Catalysis
this strategy (Scheme 2a). Based on previous
reports,[16] we attempted to synthesize alkynyl-Ge
directly from commercial available terminal alkynes.
Fortunately, when triethylamine was used as base,
terminal alkynes reacted smoothly with GeCl4 to
afford trichloro(alkynyl)germanes, which were
subsequently protected by triethanolamine analog A
obtaining diversified alkynyl-Ge in moderate to good
yields (see supporting information for details). By
this strategy, not only phenylethynyl- (2b), (4-
methoxyphenyl)ethynyl- (2c) and thiophen-2-
ylethynyl-Ge (2d), but also alkylethynyl-Ge (2e-2g)
were successfully synthesized despite of the weak
acidity of alkyl-substituted alkyne hydrogen (Scheme
2b). While 2e and 2f were obtained in good yields, 2g
was obtained in a lower yield.
N-(pivaloyloxy)benzamide (1a) and ethynyl-Ge (2a)
were chosen as model substrates to screen optimal
reaction conditions. When acetonitrile was used as
solvent and 2 equivalent of CsOAc was used as base,
a yield of 79% was obtained with a regioselectivity of
9.4/1 (3a/3a’, Table 1 entry 1).[17] However, the yield
and regioselectivity both declined when KOAc or
K2CO3 was used instead (Table 1 entries 2-3).
Replacing acetonitrile with methanol or acetone
resulted in lower yields (Table 1 entries 4-5).
Addition of AgOAc or Cu(OAc)2 failed to improve
the yield and regioselectivity (Table 1 entries 6-7). To
our delight, replacing CsOAc with CsOPiv and
adding 50 mol% Cu(OAc)2 gave the best ratio with
negligible decline in yield (Table 1 entry 8).
Table 2. The Scope of N-(Pivaloyloxy)benzamides.
Scheme 2. Preparation of Alkynyl Germatranes.
Table 1. Optimization of Reaction Conditions.
a
Reaction conditions: 1 (0.2 mmol), ethynyl germatrane 2a
(0.22 mmol), [RhCp*Cl2]2 (2.5 mol%), Cu(OAc)2 (50 mol%),
CsOPiv (0.4 mmol), CH3CN (2 mL) at room temperature for
b
16 h.
Reaction conditions: 1 (0.2 mmol), alkynyl
germatranes (0.22 mmol), [RhCp*Cl2]2 (2.5 mol%), CsOAc
(0.4 mmol), MeOH (2 mL) at room temperature for 16 h.
1
Ratios of 3 and 3’ were determined by H-NMR. The two
isomers could be separated by column chromatography.
With the optimized conditions in hand, the scope
of N-(pivaloyloxy)benzamides was investigated
(Table 2). Various electron-donating or -withdrawing
functional groups were well tolerated such as tert-
butyl (3b), methoxyl (3c, 3g), sulphonamide (3h),
bromide (3i) and sulfonyl (3j). Heterocyclic
substrates containing furan and thiophene derivatives
a)
Reaction conditions: 1a (0.2 mmol), ethynyl germatrane 2a
(0.22 mmol), [RhCp*Cl2]2 (2.5 mol%), additive (50 mol%),
base (0.4 mmol), solvent (2 mL) at room temperature for 16 h.
b) Isolated yield. c) Ratios of 3a and 3a’ were determined by
1H-NMR.
2
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10.1002/adsc.201901633
Advanced Synthesis & Catalysis
also underwent Rh(III)-catalyzed C-H activation and
annulation with ethynyl-Ge smoothly with excellent
regioselectivities (>30/1) (3d, 3e). Comparison of
different substrates indicates that the regioselectivity
was partially affected by electronic effect and steric
hindrance of the substituents on the aromatic ring.
Besides, the regioselectivities presented in Table 2
are consistent with Jones’ observations.[9c] The
regioselectivity of the alkynes insertion into C-Rh
bond is affected by both steric hindrance and
electronic effect of themselves. The steric hindrance
of ethynyl-Ge (2a) determined that 3 was the major
product. For ethynyl-Ge (2a), Ge-attaching electron-
rich end of ethynyl tends to bind with aromatic ring
when it bears electron-withdrawing substituent,
which was responsible for the decline in
regioselectivity (3h-3j). In addition, when different
alkynyl germatranes were applied, the reactions took
place smoothly to give variously substituted
isoquinolone-derived germatranes (3k-3m).
Scheme 4. Derivatization of Heterocyclic Germatranes.
With various heterocyclic germatranes in hand, we
next applied them in multiple derivatizations. Under
TBAF promoted Pd-catalyzed cross-coupling
reaction conditions,[7a] heterocyclic germatranes (3a,
3e, 5f) were successfully converted to corresponding
coupling products (6a-6d) with moderate yields
(Scheme 4A). To test the stability of isoquinolone-
derived germatranes, Suzuki-Miyaura reaction was
conducted using 3i and (4-cyanophenyl)boronic acid
as coupling partners, and desired product 6e was
obtained in which the Ge-C bond was preserved.
Furthermore, cross-coupling of 6e with aryl halides
smoothly delivered the arylated product 6f (Scheme
4B). The result suggests that isoquinolone-derived
germatranes exhibit both reactivity of cross-coupling
and unique stability under certain conditions.
Surprisingly, 3h was able to be oxidized exclusively
to monobromo-product by Br2 with excellent yield
(Scheme 4C), which further demonstrates its stability,
and following cross-coupling was able to give 6h as
product. The aforementioned results suggest that
heterocyclic germatranes are stable under Suzuki-
Miyaura cross-coupling reaction conditions but
reactive enough under certain situations, which
allows more choices for the synthesis of complex
compounds. Furthermore, under the condition of
TBAF and Pd(PPh3)2Cl2, isoquinoline-derived
germatranes could be protonated (Scheme 4D), which
provides a supplementary method for the synthesis of
isoquinoline analogues.[18]
Reaction conditions: 4 (0.2 mmol), alkynyl germatrane 2
(0.22 mmol), [RhCp*Cl2]2 (5 mol%), CsOAc or K2CO3 (0.4
mmol), CH3CN (2 mL) at 60 oC for 16 h.
Scheme 3. Synthesis of Isoquinoline-Derived Germatranes
Using Alkynyl Germatranes.
With the scope of N-(pivaloyloxy)benzamides
examined, we next changed the directing group to
highlight the versatility of this strategy. Fortunately,
target products were successfully obtained under
Rh(III)-catalyzed C-H activation and annulation
condition using diarylmethanone oximes as substrates
(Scheme 3). Not only ethynyl-Ge (2a), but also
arylethynyl-
(2b-2d),
(n-butyl)ethynyl-
and
To get insight into the reactivity of variously
substituted terminal alkynes, competition and parallel
experiments were performed (Scheme 5). In the
presence of phenylacetylene, 3a was not detected
under standard conditions, suggesting that
phenylacetylene might interfere with the coordination
of ethynyl-Ge to the Rh intermediate after C-H
(cyclopropyl)ethynyl-Ge (2e, 2f) underwent the
reaction smoothly to afford single regioisomer in
moderate to good yields (5a-5f).[18] Notably, the
BMIDA-containing analogue of 5c[10] was obtained
as a 1:1 ratio of regioisomers, which reflects the
advantage that bulkier Ge group hold regarding the
regioselectivity.
3
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10.1002/adsc.201901633
Advanced Synthesis & Catalysis
activation and subsequent migratory insertion
(Scheme 5A). Both competition and parallel
experiments revealed that the reactivity of ethynyl-Ge
is slightly lower than 1-hexyne but comparable with
ethynyl-BMIDA, which suggests that ethynyl-Ge and
ethynyl-BMIDA may exhibit similar electronic
properties. Thus, better regioselectivity of alkynyl-Ge
than alkynyl-BMIDA was observed in Scheme 3
probably owing to the greater steric hindrance of Ge.
with the release of catalyst IV reentering catalytic
circle.
In summary, we developed a strategy for the
synthesis of alkynyl germatranes, which were used in
Rh(III)-catalyzed C-H activation to generate
heterocyclic germatranes bearing various functional
groups. Furthermore, these newly explored
heterocyclic nucleophiles were proved to be versatile
in many transformations such as Suzuki-Miyaura
cross-coupling reactions and oxidizing bromination,
which makes them potential synthons for further
modifications of specific sites of heterocycles to
generate complex heterocyclic molecules.
Experimental Section
General procedure for the preparation of heterocyclic
germatranes: [RhCp*Cl2]2 (2.5 or 5 mol%), base (2 eq),
alkynyl germatrane (1.1 eq) and the corresponding C-H
substrate (1 eq) were weighed and transferred to a screw-
cap tube with stir bar. The tube was evacuated and
backfilled three times with argon, then CH3CN (0.1 M)
was added and the screw-cap tube was sealed with a
Teflon stopper and stirred at room temperature or 60 oC for
16 hours. At the end of the reaction, the reaction mixture
was filtered, and filtrate was concentrated to provide the
corresponding heterocyclic germatrane which was purified
by silica gel column chromatography.
Standard condition: 1a (0.1 mmol), terminal alkynes (0.1
mmol), [RhCp*Cl2]2 (2.5 mol%), Cu(OAc)2 (50 mol%),
CsOPiv (0.2 mmol), CH3CN (1 mL) at room temperature for
0.5 h. Yields were determined by 1H-NMR.
General procedure for cross coupling of heterocyclic
germatranes: Heterocyclic germatrane (0.1 mmol, 1.0 eq)
and Pd(PPh3)2Cl2 (5 mol%) were weighed and transferred
to a screw-cap tube with stir bar. The tube was evacuated
Scheme 5. Control Experiments.
and backfilled three times with argon, then
the
corresponding Ar-Br (0.11 mmol, 1.1 eq) and 2-
methyltetrahydrofuran (0.3 mL) were added, followed by
the solution of TBAF-H2O (0.4 mmol, 4.0 eq, 1.22 M in 2-
methyltetrahydrofuran) in 2-methyltetrahydrofuran. The
screw-cap tube was sealed with a Teflon stopper and
stirred at 80 oC for 16 hours. At the end of the reaction, the
reaction mixture was concentrated to provide isoquinolone
or isoquinoline derivative which was purified by silica gel
column chromatography.
Acknowledgements
We thank the NSFC (21871239) and Youth Innovation Promotion
Association of the Chinese Academy of Sciences (2015371) for
financial support.
References
Scheme 6. Proposed Mechanism.
On the basis of previous reports,[10,11] plausible
mechanism was proposed (Scheme 6). At beginning,
intermediate I was generated from directed Rh-
catalyzed C-H activation accompanied by the release
of two molecules of HOPiv. Following coordination
of alkynyl germatrane with intermediate I took place
to form intermediate II, which was followed by
insertion of alkynes into Rh-C bond, generating
intermediate III. Subsequent reductive elimination
with the aid of HOPiv gave target product 3, along
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10.1002/adsc.201901633
Advanced Synthesis & Catalysis
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10.1002/adsc.201901633
Advanced Synthesis & Catalysis
[17] The crystallographic data of 3a are available free of
charge from the Cambridge Crystallographic Data
Centre under accession number CCDC-1878702.
[18] The structures of 5b-5f were confirmed by comparing
NMR and mass spectra of degermatrane-protonation
derivatives of 5b-5f with known compounds. S. S.
Zhang, X. G. Liu, S. Y. Chen, D. H. Tan, C. Y. Jiang, J.
Q. Wu, Q. J. Li, H. G. Wang, Adv. Synth. Catal. 2016,
358, 1705. Please see supporting information for details.
6
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Advanced Synthesis & Catalysis
UPDATE
Synthesis and Application of Heterocyclic
Germatranes via Rhodium-Catalyzed Directed C-H
Activation/Annulation with Alkynyl Germatranes
and Palladium-Catalyzed Cross-Coupling
Adv. Synth. Catal. Year, Volume, Page – Page
Meng-Yu Xu, Chao Wang, Wei-Tao Jiang and Bin
Xiao*
7
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