Rhodium-Catalyzed Arylative Transformations of Propargylic Diols: Dual Role of the Rhodium Catalyst

Article abstract of DOI:10.1002/adsc.201800048

Controllable synthesis of a variety of allenic alcohols and 2,5-dihydrofurans by rhodium(I)-catalyzed arylative transformations of propargylic diols is reported. The hydroxorhodium catalyst was found to play dual role: it catalyzed the arylation/dehydroxylation reaction of propargylic diols to afford allenic alcohols, and besides, it could convert to a cationic rhodium species in situ, which catalyzed the intramolecular hydroalkoxylation of allenic alcohols to form dihydrofurans. Remarkably, generation of the cationic rhodium species is dependent on the arylboron reagent used. Thus, the controllable synthesis is achieved by simply changing the arylboron reagent. (Figure presented.).

Full text of DOI:10.1002/adsc.201800048

Title: Rhodium-Catalyzed Arylative Transformations of Propargylic
Diols: Dual Roles of the Rhodium Catalyst
Authors: Junhao Xing, Yong Zhu, Xiao Lin, Na Liu, Yue Shen, Tao Lu,
and Xiaowei Dou
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10.1002/adsc.201800048
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Rhodium-Catalyzed Arylative Transformations of Propargylic
Diols: Dual Role of the Rhodium Catalyst
Junhao Xing,a,# Yong Zhu,a,# Xiao Lin,a Na Liu,a Yue Shen,a Tao Lu,a,b and Xiaowei
Doua,*
a
Department of Organic Chemistry, School of Science, China Pharmaceutical University, 639 Longmian Avenue,
Nanjing 211198, China
b
State Key Laboratory of Natural Medicines, China Pharmaceutical University, 24 Tongjiaxiang, Nanjing 210009,
China
#
These authors contributed equally
Fax: (+86)-25-8618-5179; e-mail: dxw@cpu.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######.
convert to a cationic rhodium species under suitable
alcohols and 2,5-dihydrofurans by rhodium(I)-catalyzed reaction conditions to promote new transformations
Abstract. Controllable synthesis of a variety of allenic
arylative transformations of propargylic diols is reported.
The hydroxorhodium catalyst was found to play dual role:
it catalyzed the arylation/dehydroxylation reaction of
propargylic diols to afford allenic alcohols, and besides, it
could convert to a cationic rhodium species in situ, which
catalyzed the intramolecular hydroalkoxylation of allenic
alcohols to form dihydrofurans. Remarkably, generation of
the cationic rhodium species is dependent on the arylboron
reagent used. Thus, the controllable synthesis is achieved
by simply changing the arylboron reagent.
(Scheme 1a). This serendipitous finding originated
from the study of the rhodium-catalyzed arylative
transformations of propargylic diols, and eventually
led to a controllable synthesis of a series of fully
substituted allenic alcohols[4] and 2,5-dihydrofurans[5]
(Scheme 1b).
Keywords: rhodium; propargylic diol; arylation; allenes;
dihydrofuran
The metal catalyst, which plays an essential role in
the metal-catalyzed transformations, may show
disparate catalytic activities when existing in
different forms, and thus greatly affects the reaction
pathway and outcomes.[1] As a result, a thorough
understanding of the metal catalyst, especially its
existing forms during the reaction, is of great
significance for development of metal catalysis. As
one of the most convenient and reliable methods for
the construction of C–C bonds, the rhodium(I)-
catalyzed arylation reactions of unsaturated bonds
with arylboron reagents have been extensively
explored over the last decades.[2] In particular, the
detailed reaction pathway of rhodium(I)-catalyzed
arylation reactions with arylboron reagent was
studied,[2,3] and it is well accepted that the rhodium(I)
catalyst participates in the catalytic cycle via
transmetalation with arylboron reagent to form an
arylrhodium species. However, the possibility of the
rhodium catalyst to form other catalytically active
species during the reaction is neglected. Herein, we
report our finding that the hydroxorhodium catalyst
can not only catalyze the arylation process, but also
Scheme 1. Dual role of the rhodium catalyst and divergent
transformations of propargylic diols.
Propargylic 1,4-diols are attractive substrates for
organic synthesis in terms of availability and
economy, since they are bench stable, inexpensive,
and easily prepared from abundant acetylene and
ketones. However, the transformations of propargylic
diols were mainly restricted to cyclization reactions
to furnish heterocyclic compounds.[6] Recently,
Sherburn and co-workers developed an elegant
palladium-catalyzed Suzuki–Miyaura-like cross-
coupling of propargylic diols to prepare 1,3-
butadienes or allenic alcohols,[7] which greatly
expanded the synthetic utilities of those readily
available reagents (Scheme 2). This palladium-
catalyzed reaction provided a novel and reliable
method for the synthesis of a series of 1,3-butadienes
via twofold cross-coupling and allenic alcohols via
1
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10.1002/adsc.201800048
Advanced Synthesis & Catalysis
single cross-coupling, respectively. However, there
are still several challenges to be addressed. For
example, the direct twofold cross-coupling could only
introduce the same substitution group at 2,3-positions
on the final products, hence limited the diversity of
1,3-butadienes accessible. Moreover, the allenic
alcohol synthesis was only applicable to the bulky
substrates (bulky diols or bulky aryl boronic acids
should be used), and other substrates were not able to
stop at the allenic alcohol step, but directly underwent
twofold cross-couplings. We then envisaged that a
selective and stepwise synthesis may overcome the
aforementioned limitations. For instance, a suitable
metal catalysis may provide a general method to
access allenic alcohols, which could be further
transformed to dienes bearing different substitutions
by the palladium-catalyzed cross-coupling.[8] As part
of our ongoing interests in the transformations of
propargylic alcohols,[9] we embarked on a project
aiming at the general and selective synthesis of
allenic alcohols from propargylic diols and their
further transformations to unsymmetrical 1,3-
butadienes (Scheme 2).
propargylic diols prepared from diverse ketones were
well-tolerated (3i–3p). In particular, when
unsymmetrical diols were used, the aromatic ring was
introduced preferentially to the less hindered side
(3n–3p). It should be noted that most of the allenic
alcohols reported here are not accessible by the
previous method.[7] Using 3a as the model substrate,
we verified our hypothesis that unsymmetrical 1,3-
butadienes could be achieved selectively (Scheme 4).
Scheme 3. Scope of the allenic alcohol synthesis.
Scheme 2. Synthesis of allenic alcohols and 1,3-butadienes
from propargylic diols.
Our group is particularly interested in the rhodium-
catalyzed transformations of propargylic alcohols,[9]
and we recently developed a rhodium(I)-catalyzed
arylation reaction of -alkyl tert-propargylic alcohols
for the synthesis of allenes.[9a] We then speculated
that this method might be amendable to the synthesis
of allenic alcohols from propargylic diols. However,
the challenge is the bulkiness associated with the tert-
propargylic diols, which is not favourable for the
projected arylation reaction. Nevertheless, we
commenced our study by investigating the arylation
of tert-propargylic diol 1a. To our delight, the
reaction proceeded smoothly with [Rh(OH)(cod)]2 as
the catalyst, and when phenylboronic acid
neopentylglycol ester 2a was used as the arylboron
reagent,[10] the desired allenic alcohol product 3a was
obtained in 89% yield. The generality of the reaction
was then investigated. As shown in Scheme 3,
diverse arylboronic acid neopentylglycol esters,
including those bearing substitutions with both
Scheme 4. Cross-coupling of 3a to unsymmetrical dienes.
During our study of the model reaction between
propargylic diol 1a and various phenylboron reagents.
It was found that divergent reaction outcomes were
obtained when different phenylboron reagents were
used (see Table S1 in the Supporting Information for
details). For example, when phenylboronic acid
neopentylglycol ester 2a was used, allenic alcohol 3a
was formed exclusively. However, under otherwise
identical reaction conditions, replacement of 2a with
phenylboronic acid 5a resulted in the formation of
dihydrofuran 6a as the sole product (Scheme 5).
electron-donating
and
electron-withdrawing
characters, halogen substitutions, as well as
heterocyclic arylboron reagent, were all suitable in
this reaction system (3a–3h). Besides, different
Scheme 5. Divergent products with different arylborons.
2
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10.1002/adsc.201800048
Advanced Synthesis & Catalysis
In the literature precedence, combination of the
chloride catalyst, which was used in Breit’s system,
the reaction did not proceed at all (entry 5). Further
studies of other conditions[12] to produce the
rhodium(III) hydride species all failed to enable the
reaction (entry 6, see Table S2 in the Supporting
Information for more conditions). Being aware that
the hydroxorhodium is slightly basic[13] while boric
acid is a weak acid, we then considered the
possibility of a simple acid-base reaction to form a
same rhodium catalyst with different arylboron
reagents usually led to the change of reactivity, rather
than the reaction pathway.[2,10] We speculated that
there should be different catalytically active species
present in the reaction system when different
arylboron reagents were used. Thus, these
extraordinary results prompted us to further
investigate the reasons behind.
cationic tetrahydroxoborato-rhodium(I) complex
–
Table 1. Intramolecular hydroalkoxylation of allenic
alcohol 3a.[a]
[Rh(cod)]+B(OH)4
in
equilibrium,[14]
which
accounted for the observed cyclization reaction.
Indeed, the cationic rhodium catalyst, either
preformed or generated in situ, facilitated the
conversion of 3a to 6a without additives (entries 7 &
8). The possibility of boric acid simply serving as a
proton donor[15] was also excluded as no additional
proton donor was required for this transformation
(entries 7 & 8). To further validate our conclusion,
boric acid was introduced as the additive to the
reactions in Scheme 5, and as anticipated,
dihydrofuran 6a was formed exclusively regardless of
the arylboron reagent used (eq 1). To our delight,
with the additional boric acid, 6a could be obtained
quantitatively using phenylboronic acid as the aryl
source.
Entry
Conditions
Yield [%][b]
1
2
3
4
[Rh(OH)(cod)]2 (5 mol % Rh)
PhB(OH)2 (1 equiv.)
B(OH)3 (1 equiv.)
[Rh(OH)(cod)]2 (5 mol % Rh)
+ B(OH)3 (1 equiv.)
n.r.
n.r.
n.r.
83
5
6
[RhCl(cod)]2 (5 mol % Rh)
+ B(OH)3 (1 equiv.)
n.r.
n.r.
[RhCl(cod)]2 (5 mol % Rh)
+ PhCO2H (10 mol %)
[Rh(cod)2]BF4 (5 mol % Rh)
[RhCl(cod)]2 (5 mol % Rh)
+ AgBF4 (5 mol %)
7
8
84
78
[a]
[b]
The reactions were carried out with 3a (0.20 mmol)
under indicated conditions.
Isolated yield of 6a. n.r.: no reaction.
For the reaction producing 6a as the final product,
both 6a and 3a could be detected at the early stage.
Thus, we hypothesized that dihydrofuran 6a was
formed by the intramolecular hydroalkoxylation of
allenic alcohol 3a,[5] and various conditions were
investigated to identify the species which enabled the
transformation. As shown in Table 1, neither the
hydroxorhodium catalyst nor the phenylboronic acid
promoted the reaction (entries 1 & 2). Boric acid was
generated during the arylation reaction when
phenylboronic acid was used, so it was tested as the
additive. Surprisingly, although the boric acid itself
was not catalytically active (entry 3), its combination
with the hydroxorhodium catalyst efficiently
promoted the formation of 6a (entry 4). Inspired by
Scheme 6. Scope of the 2,5-dihydrofuran synthesis.
The scope of the dihydrofuran synthesis was then
examined, which is summarized in Scheme 6.
Arylboronic acids bearing electron-donating or
electron-withdrawing substitutions and halogen
substitutions at different positions on the phenyl ring,
as well as other types of arylboronic acids were all
suitable in this reaction system, and delivered the
desired 2,5-dihydrofurans in high efficiency (6a–6h,
up to 99% yield). The structure of the dihydrofuran
products was unambiguously confirmed by single-
crystal X-ray diffraction analysis of 6g.[16] In addition
Breit’s
work
on
the
rhodium-catalyzed
hydroalkoxylation of allenes,[11] we initially
hypothesized that the reaction might proceed via a
rhodium(III) hydride intermediate, which might be
generated by oxidative addition of rhodium(I) to the
boric acid O–H bond. However, when the
hydroxorhodium catalyst was changed to the rhodium
3
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10.1002/adsc.201800048
Advanced Synthesis & Catalysis
(1.0 mL) was added and the resulting solution was stirred
to various arylboronic acids, propargylic diols
derived from diverse alkyl ketones worked well under
optimal reaction conditions (6i–6m). However, as a
limitation of current method, when propargylic diols
bearing aromatic substitutions were employed, the
reaction did not proceed further to give the
dihydrofurans, but yielded allenic alcohols as the
major product (6n–6o).
o
at 80 C for 12 h. Upon completion, the reaction was
diluted with water (5 mL), and extracted with ethyl acetate
(5 mL*2). The organic phase was combined and the
solvent was removed on a rotary evaporator. The crude
product was subjected to silica gel chromatography with
petroleum ether/ethyl acetate (20/1) to give allenic alcohol
3.
General Procedure for the Synthesis of 2,5-
Dihydrofurans.
Based on the experimental results and literature
precedence, a plausible mechanism of the reaction
was proposed. As illustrated in Scheme 7, the
arylrhodium intermediate was first generated by
transmetalation of the hydroxorhodium catalyst with
arylboron reagents,[3] followed by an arylrhodation/-
OH elimination process[9a,17] to furnish allenic
alcohols 3. In the presence of boric acid (generated in
situ or added as the additive), a cationic rhodium
[Rh(OH)(cod)]2 (2.3 mg, 5 mol, 5 mol % Rh),
propargylic diol 1 (0.20 mmol), boric acid (0.20 mmol),
and arylboronic acid 5 (0.30 mmol) were placed in an
oven-dried Schlenk tube under nitrogen. Anhydrous THF
(1.0 mL) was added and the resulting solution was stirred
o
at 80 C for 12 h. Upon completion, the reaction was
diluted with water (5 mL), and extracted with ethyl acetate
(5 mL*2). The organic phase was combined and the
solvent was removed on a rotary evaporator. The crude
product was subjected to silica gel chromatography with
petroleum ether/ethyl acetate (40/1) to give 2,5-
dihydrofuran 6.
–
complex [Rh(cod)]+B(OH)4 was assumed to be
formed, which served as the Lewis acid catalyst to
promote the intramolecular hydroalkoxylation of
allenic alcohols to generate dihydrofurans.[5]
Acknowledgements
We are grateful for the financial support from the National
Natural Science Foundation of China (21602253) and the
Natural Science Foundation of Jiangsu Province (BK20160749).
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Advanced Synthesis & Catalysis
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5
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Advanced Synthesis & Catalysis
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Rhodium-Catalyzed Arylative Transformations of
Propargylic Diols: Dual Role of the Rhodium
Catalyst
Adv. Synth. Catal. Year, Volume, Page – Page
Junhao Xing,# Yong Zhu,# Xiao Lin, Na Liu, Yue
Shen, Tao Lu, and Xiaowei Dou*
6
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