Rhodium-Catalyzed Diverse Arylation of 2,5-Dihydrofuran: Controllable Divergent Synthesis via Four Pathways

Article abstract of DOI:10.1021/acscatal.0c00265

The rhodium-catalyzed controllable diverse arylation of 2,5-dihydrofuran with arylboronic acids is reported. By fine-tuning of the reaction conditions, four different ring-opening or oxidative arylation pathways are controlled in the rhodium-catalyzed ary

Full text of DOI:10.1021/acscatal.0c00265

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Letter
Rhodium-Catalyzed Diverse Arylation of 2,5-Dihydrofuran:
Controllable Divergent Synthesis via Four Pathways
Junhao Xing, Wanjiang Zhu, Bihai Ye, Tao Lu, Tamio Hayashi,* and Xiaowei Dou*
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ABSTRACT: The rhodium-catalyzed controllable diverse aryla-
tion of 2,5-dihydrofuran with arylboronic acids is reported. By fine-
tuning of the reaction conditions, four different ring-opening or
oxidative arylation pathways are controlled in the rhodium-
catalyzed arylation of 2,5-dihydrofuran, granting selective access
to 2-aryl or 3-aryl homoallylic alcohols and 3-aryl or 4-aryl-2,3-
dihydrofurans. The catalytic asymmetric ring-opening arylation of
2,5-dihydrofuran was also realized. Four plausible reaction
pathways were proposed, based on the experimental results.
KEYWORDS: rhodium, arylation, divergent synthesis, dihydrofuran, reaction pathway
he efficient production of structurally diverse compounds
phospholene oxides9c have been investigated, and hydro-
Tremains an important goal in organic synthesis. In this arylation products were obtained in all of the cases. In the
series of 5-membered heterocyclic alkenes, 2,5-dihydrofuran
(2,5-DHF) remains the most challenging substrate, as it is not
feasible to adjust the reactivity and selectivity of the substrate
by varying the protecting group or by isomerization of the
olefin.9 Herein, we report our latest progress on the rhodium-
catalyzed arylation of 2,5-DHF. Remarkably, the reaction did
not give the hydroarylation product, but gave diverse ring-
opening or oxidative arylation products under different
reaction conditions. Two types of ring-opening arylation
products and two types of oxidative arylation products were
selectively produced (see Scheme 1b). In addition, the
asymmetric ring-opening arylation of 2,5-DHF was also
realized.
We commenced our investigation with 2,5-DHF (1a) and
phenylboronic acid (2a), and some key results are summarized
in Table 1. The reaction was first conducted in dioxane with
cyclooctadiene (cod)-coordinated rhodium as the catalyst, and
the reaction produced a mixture of three ring-opening products
(3a, Z-4a, and E-4a) (Table 1, entry 1).10 Replacing cod by
bisphosphine ligands resulted in the selective formation of 3a,
but only in trace amounts (Table 1, entries 2−4). When the
reaction was conducted in aqueous dioxane, the cod-ligated
catalyst led to no phenylation products due to complete
protodeboronation of 2a, while another ring-opening product
5a was selectively formed with the binap-ligated rhodium
regard, the divergent synthesis represents a useful approach to
achieving molecule diversity. By appropriate modifications of
the catalyst or reaction parameters, diverse products can be
generated from a single starting material.1 From a practical
point of view, it is desirable to selectively achieve as many as
possible different types of products from a given reaction.
However, because of the difficulties in controlling the elusive
chemoselectivities and regioselectivities, the known divergent
synthesis usually gives maximum two types of products.1,2
Herein, we report an unprecedented rhodium-catalyzed diverse
arylation reaction, which selectively produces four structurally
divergent products from one single substrate, demonstrating
the great potency of rhodium-catalyzed arylation in divergent
synthesis.
The rhodium-catalyzed reaction of alkenes with arylboronic
acids has emerged as a useful method in organic synthesis, and
various arylation products are obtained via different pathways.3
For example, in addition to the classical hydroarylation
products,4 some alkenes may undergo oxidative arylation to
give the Heck-type products,5 and the formal allylic arylation
products can be produced via β-X (X = O, F, etc.) elimination6
(see Scheme 1a). However, these pathways are usually
substrate-dependent, and examples on the rhodium-catalyzed
divergent arylation of a given alkenyl substrate are rare.7 In
recent years, there has been great interest in applying rhodium-
catalyzed arylation to unactivated alkenes.8 We have been
interested in studying the rhodium-catalyzed arylation of
heterocyclic alkenes for synthesizing 5-membered heterocyclic
rings, which are important structural motifs present in
numerous pharmaceutical drugs and natural products. In our
previous studies, 3-pyrrolines,9a cyclic allyl sulfones,9b and
Received: January 16, 2020
Revised: February 8, 2020
Published: February 12, 2020
https://dx.doi.org/10.1021/acscatal.0c00265
© XXXX American Chemical Society
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Scheme 1. Rhodium-Catalyzed Diverse Arylation of
Alkenes: (a) Product Diversity in Rhodium-Catalyzed
Arylation of Alkenes and (b) Rhodium-Catalyzed Arylation
of 5-Membered Heterocyclic Alkenes
Table 1. Rhodium-Catalyzed Phenylation of 2,5-DHF (1a)
with Phenylboronic Acid (2a)
a
b
c
entry
conditions
dioxane
dioxane/binap
product(s)
yield (%)
1
2
3
4
5
6
7
8
9
3a:Z-4a:E-4a = 1:0.12:0.08
47
5
<3
<3
−
82
60
86
35
31
34
96
75
d
3a
3a
3a
d
dioxane/dppe
d
dioxane/dppf
dioxane/H2O
no phenylation product
d
dioxane/H2O/binap
THF
THF/H2O/binap
tBuOH
iPrOH
EtOH
5a
3a:Z-4a:E-4a = 1:0.17:0.05
d
5a
6a
7a
7a
3a
6a
7a
10
11
12
13
14
e
THF (1a:2a = 3:1)
tBuOH (1a:2a = 3:1)
e
f
g
EtOH (1a:2a = 1:3)
92
a
Reaction conditions: 1a (0.20 mmol), 2a (0.30 mmol), catalyst (5
mol % Rh), and solvent (1.0 mL, 50 μL of H2O if used), 55 °C, 12 h.
b
c
Determined by 1H NMR analysis. Isolated yield of combined
d
products. [Rh(OH)(coe)2]2 (5 mol % Rh) and phosphine ligand (6
mol %). Reaction time was 24 h. Run at 70 °C. Calculated based on
the theoretical amount of product.
e
f
g
catalyst (Table 1, entries 5 and 6). The same products were
obtained in higher yields with THF as the solvent, and 5a was
selectively produced as the sole product in 86% yield (Table 1,
entries 7 and 8). The possible formation of bisphosphine
monoxide under aqueous conditions was excluded,11 since the
control experiment using binap(O) as a ligand gave no
phenylation product. Further studies on the solvent effect
revealed a significant solvent-dependent product selectivity,
and oxidative arylation products 6a and 7a were formed in
alcohols. Interestingly, 3-phenyl-2,3-DHF 6a was selectively
formed in tertiary butanol (Table 1, entry 9), while the
reactions in ethanol and isopropanol gave 4-phenyl-2,3-DHF
7a selectively (Table 1, entries 10 and 11). Reaction
parameters including temperature, concentration, reaction
time, and substrate ratio were screened to improve the yield
and selectivity. An excess amount of 2,5-DHF was found to be
beneficial to achieve excellent chemoselectivity and higher
yield in the synthesis of 3a and 6a. With a molar ratio of 1a:2a
= 3:1, 3a was produced selectively in 96% yield (Table 1, entry
12), and the yield of 6a was improved to 75% (Table 1, entry
13). Because of the fast competing protodeboronation, an
excess amount of 2a was used for the production of 7a (Table
1, entry 14). It is noteworthy that exclusive product selectivity
was observed in entries 8−14 in Table 1, and the other
phenylation products were not detected at all via TLC and 1H
NMR analysis.
Scheme 2. Formation of Products 3a and 4a
The formation of diverse products under different reaction
conditions prompted us to consider the plausible reaction
pathway. As shown in Scheme 2, path A may account for the
formation of 3a: syn insertion of 2,5-DHF to the phenyl-
rhodium species generates the key intermediate I, which
undergoes sequential β-oxygen elimination, transmelation, and
final hydrolysis (during workup) to give 3a. The product of
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a
Scheme 3. Formation of Product 6a
Table 2. Divergent Synthesis of Homoallylic Alcohols
Scheme 4. Formation of Products 5a and 7a
a
Reaction conditions to produce 3: 1a (0.60 mmol), 2 (0.20 mmol),
[Rh(OH)(cod)]2 (5 mol % Rh), and THF (1.0 mL), 55 °C, 24 h;
reaction conditions to produce 5: 1a (0.20 mmol), 2 (0.30 mmol),
[Rh(OH)(coe)2]2 (5 mol % Rh), binap (6 mol %), and THF/H2O
(1.0 mL/50 μL), 55 °C, 12 h.
recoordination of the [Rh]−H from one olefin face to the
other; the other one involves ion pair III as an intermediate,
which enables the interconversion between II and IV. Once
[Rh] moved to the other face, it leads to thermodynamically
more stable benzyl-Rh intermediate V. It is noteworthy that
these two pathways involve the movement of different
hydrogens, which indicates that the reaction using a deuterated
substrate can give significant information on the reaction
pathway. The deuterium labeling experiment was conducted
with 1a-d2, and both 7a-d2 and 5a-d2 were obtained selectively
under established reaction conditions. The deuterium dis-
tribution in 7a-d2 and 5a-d2 is in good agreement with pathway
2; therefore, the possibility of pathway 1 is tentatively
excluded.12 The polar solvents may stabilize ion pair (III) to
promote the coordination site change, which explains the
formation of 5a and 7a in aqueous solvents and polar alcohols.
Again, alcohol solvents can inhibit the β-oxygen elimination or
they can promote the olefin dissociation, such as that observed
in the case of the formation of 6a, thus leading to the
formation of 7a.
With the conditions of entries 8 (product 5), 12 (product
3), 13 (product 6), and 14 (product 7) in Table 1 as the
optimal conditions, we next investigated the scope of the
rhodium-catalyzed diverse arylation of 2,5-DHF. As shown in
Table 2, the divergent synthesis of 2- and 3-substituted
homoallylic alcohols (3 and 5) was first studied. Arylboronic
acids bearing electron-donating groups, halides, and electron-
withdrawing groups at the para-position (3b−3j, 5b−5j) or
the meta-position (3k−3o, 5k−5o) were all suitable. The bis-
deuterium labeling experiment (1a-d2 to 3a-d2) is consistent
with the proposed pathway. The formation of 4a is attributed
to the Rh-catalyzed isomerization of 1a into 2,3-dihydrofuran
(1b) during the reaction, the latter giving 4a through the
phenylrhodation/β-oxygen elimination pathway. The intermo-
lecular competition reaction reveals that 1a is more reactive
than 1b for the phenylation reaction, which, in part, explains
the inhibition of side product 4a with an excess amount of 1a.
As shown in Scheme 3, the intermediate I can also undergo
syn β-hydrogen elimination to form II, and DHF 1a (or
alcohol) attacks [Rh] to dissociate 6a by an associative
mechanism. One interesting finding is that alcohol solvents can
inhibit the β-oxygen elimination from I or they can promote
the olefin dissociation from II, thus avoiding the formation of
3a. The pathway giving 6a is consistent with the deuterium
labeling experiment (Scheme 3) and the experimental result
that the yield is higher with an excess amount of 2,5-DHF.
The formation of products 5a and 7a is supposed to
originate from the same intermediate V, which can undergo β-
oxygen elimination or β-hydrogen elimination to produce 5a
or 7a, respectively (see Scheme 4). As illustrated in Scheme 4,
the formation of intermediate V involves the movement of
[Rh] from one olefin face to the other face, i.e., from
intermediate II to intermediate IV. There are two possible
pathways for the formation of IV: the first one is dissociation/
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a
a
Table 3. Divergent Synthesis of 2,3-Dihydrofurans
Table 4. Asymmetric Ring-Opening Arylation of 2,5-DHF
a
Reaction conditions: 1a (0.60 mmol), 2 (0.20 mmol), catalyst (10
mol % Rh), and 1,4-dioxane (1.0 mL), 55 °C, 24 h. The catalyst was
generated in situ from [Rh(OH)(coe)2]2 and (R)-segphos, and the
catalyst was added in two portions.
substitutions at different positions tolerated (6b−6n). Multi-
substituted arylboronic acids (6o−6q), naphthylboronic acids
(6r−6s), and 1-cyclohexenylboronic acid (6t) were all suitable.
The selective synthesis of 4-aryl 2,3-DHFs was also feasible,
albeit with a limited scope of arylboronic acids. As shown in
Table 3, the reaction worked well for the para-substituted
(7b−7f) and bis-meta-substituted arylboronic acids (7g and
7h).
a
Reaction conditions to produce 6: 1a (0.60 mmol), 2 (0.20 mmol),
t
[Rh(OH)(cod)]2 (5 mol % Rh), and BuOH (1.0 mL), 55 °C, 24 h.
Reaction conditions to produce 7: 1a (0.20 mmol), 2 (0.60 mmol),
[Rh(OH)(cod)]2 (5 mol % Rh), and EtOH (1.0 mL), 70 °C, 12 h.
Chiral homoallylic alcohols are highly important synthons
for asymmetric synthesis. The catalytic asymmetric ring-
opening of 2,5-DHF with alkyl Grignard reagents to give 2-
alkyl homoallylic alcohols has been developed,15 but the
asymmetric ring-opening with aryl nucleophiles remained
elusive.16 After extensive studies on the reaction parameters,
the rhodium-catalyzed asymmetric arylative ring opening of
2,5-DHF was successfully realized (see Table S1 in the
Supporting Information for details of optimization).17 As
summarized in Table 4, most of the arylboronic acids worked
well to give the chiral homoallylic alcohols in high yields with
good to excellent enantioselectivities (average enantiomeric
excess (ee) of 86% for 16 examples), regardless of electron-
donating or electron-withdrawing substitutions. Lower enan-
tioselectivities (59% to 72% ee) were observed with halide-
substituted arylboronic acids, but the 3,5-F-substituted one
showed excellent enantioselectivity (98% ee). The enantioen-
riched product 3a was determined to be of R-configuration by
comparison of its specific rotation with that reported,18 and the
absolute configurations of other products were assigned by
analogy.
substituted arylboronic acids (3p−3r, 5p−5r) and 2-
naphthylboronic acid (3s, 5s) also worked well. In addition,
1-cyclohexenylboronic acid was tolerated (3t, 5t). All the
examples produced the divergent ring-opening products in
high yields with perfect chemoselectivities.
Substituted 2,3-DHFs have been regarded as an important
class of organic compounds; however, available methods to
accessing 3- and 4-substituted 2,3-DHFs are very limited.13,14
The Heck-type reaction of 2,5-DHF usually failed to give the
3-substituted 2,3-DHFs, as a result of the Pd−H-mediated
isomerization of 2,5-DHF to 2,3-DHF.13b The known methods
to 4-substituted 2,3-DHFs either required a stoichiometric
amount of palladium complex14a or suffered from multistep
synthesis.14b To remedy these methodological deficiencies, we
continued to investigate the divergent synthesis of 3- and 4-
substituted 2,3-DHFs (6 and 7). As shown in Table 3, the
oxidative arylation of 2,5-DHF to give 3-aryl 2,3-DHFs showed
a wide scope, with arylboronic acids bearing various
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Letter
Beletskaya, I. P.; Yus, M. Metal-Catalyzed Regiodivergent Organic
Reactions. Chem. Soc. Rev. 2019, 48, 4515−4618.
In summary, we have developed a rhodium-catalyzed diverse
arylation reaction of 2,5-dihydrofuran. By appropriate mod-
ifications of the reaction conditions, the reaction pathway was
perfectly controlled to produce each of the four products with
high selectivity (>99%). The asymmetric version of the ring-
opening arylation reaction was also realized. The reported
transformations not only provide effective approaches to some
synthetically useful compounds, but also demonstrate the great
potency of rhodium-catalyzed arylation in divergent synthesis.
(2) A palladium-catalyzed divergent synthesis producing four
products was reported; see: Wang, M.; Zhang, X.; Zhuang, Y.-X.;
Xu, Y.-H.; Loh, T.-P. Pd-Catalyzed Intramolecular C-N Bond
Cleavage, 1,4-Migration, sp3 C-H Activation, and Heck Reaction:
Four Controllable Diverse Pathways Depending on the Judicious
Choice of the Base and Ligand. J. Am. Chem. Soc. 2015, 137, 1341−
1347.
(3) For reviews, see: (a) Fagnou, K.; Lautens, M. Rhodium-
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T.; Yamasaki, K. Rhodium-Catalyzed Asymmetric 1,4-Addition and
Its Related Asymmetric Reactions. Chem. Rev. 2003, 103, 2829−2844.
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Synthetic Applications of Rhodium Catalysed Conjugate Addition.
Chem. Soc. Rev. 2010, 39, 2093−2105. (d) Tian, P.; Dong, H.-Q.; Lin,
G.-Q. Rhodium-Catalyzed Asymmetric Arylation. ACS Catal. 2012, 2,
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2017, 15, 1029−1050. (f) Jia, T.; Cao, P.; Liao, J. Enantioselective
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(6) For selected examples, see: (a) Menard, F.; Chapman, T. M.;
Dockendorff, C.; Lautens, M. Rhodium-Catalyzed Asymmetric Allylic
Substitution with Boronic Acid Nucleophiles. Org. Lett. 2006, 8,
4569−4572. (b) Miura, T.; Ito, Y.; Murakami, M. Synthesis of gem-
Difluoroalkenes via β-Fluoride Elimination of Organorhodium(I).
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Funaki, K.; Sato, T.; Oi, S. Rhodium-Catalyzed Asymmetric Coupling
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Rhodium-Catalysed Asymmetric Allylic Arylation of Racemic Halides
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.0c00265.
■
sı
Experimental procedures, characterization data, copies of
1H and 13C NMR spectra, and HPLC charts (PDF)
AUTHOR INFORMATION
Corresponding Authors
■
Tamio Hayashi − Department of Chemistry and Biological
Chemistry, School of Physical and Mathematical Sciences,
Nanyang Technological University, Singapore 637371
Singapore; orcid.org/0000-0001-9187-3664;
Email: tamio.hayashi@gmail.com
Xiaowei Dou − Department of Chemistry and State Key
Laboratory of Natural Medicines, China Pharmaceutical
University, Nanjing 211198, China; orcid.org/0000-0002-
0748-1279; Email: dxw@cpu.edu.cn
Authors
Junhao Xing − Department of Chemistry and State Key
Laboratory of Natural Medicines, China Pharmaceutical
University, Nanjing 211198, China
Wanjiang Zhu − Department of Chemistry and State Key
Laboratory of Natural Medicines, China Pharmaceutical
University, Nanjing 211198, China
Bihai Ye − Department of Chemistry and State Key Laboratory
of Natural Medicines, China Pharmaceutical University,
Nanjing 211198, China
Tao Lu − Department of Chemistry and State Key Laboratory of
Natural Medicines, China Pharmaceutical University, Nanjing
211198, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.0c00265
Notes
The authors declare no competing financial interest.
̈
with Arylboronic Acids. Nat. Chem. 2015, 7, 935−939. (f) Schafer, P.;
Palacin, T.; Sidera, M.; Fletcher, S. P. Asymmetric Suzuki-Miyaura
Coupling of Heterocycles via Rhodium-Catalysed Allylic Arylation of
Racemates. Nat. Commun. 2017, 8, 15762.
ACKNOWLEDGMENTS
■
We thank the financial support from the National Natural
Science Foundation of China (Nos. 81903459 and 21602253),
the Natural Science Foundation of Jiangsu Province (No.
BK20180572), and the “Double First-Class” University project
(Nos. CPU2018GY35 and CPU2018GF02).
(7) (a) Shintani, R.; Duan, W.-L.; Hayashi, T. Rhodium-Catalyzed
Asymmetric Construction of Quaternary Carbon Stereocenters:
Ligand-Dependent Regiocontrol in the 1,4-Addition to Substituted
Maleimides. J. Am. Chem. Soc. 2006, 128, 5628−5629. (b) Menard,
F.; Lautens, M. Chemodivergence in Enantioselective Desymmetriza-
tion of Diazabicycles: Ring-Opening versus Reductive Arylation.
Angew. Chem., Int. Ed. 2008, 47, 2085−2088. (c) Panteleev, J.;
Menard, F.; Lautens, M. Ligand Control in Enantioselective
Desymmetrization of Bicyclic Hydrazines: Rhodium(I)-Catalyzed
Ring-Opening versus Hydroarylation. Adv. Synth. Catal. 2008, 350,
2893−2902. (d) Claraz, A.; Serpier, F.; Darses, S. Organoboron
Initiated Rh-Catalyzed Asymmetric Cascade Reactions: A Subtle
Switch in Regioselectivity Leading to Chiral 3-Benzazepine Deriva-
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