Dirhodium(II)-Catalyzed Cyclopropanation of Alkyne-Containing α-Diazoacetates for the Synthesis of Cycloalkynes

Article abstract of DOI:10.1002/adsc.202000360

An efficient dirhodium(II)-catalyzed macrocyclization reaction of alkyne-containing diazoacetates through intramolecular metal carbene cyclopropanation is described. This method provides a variety of 12- to 22-membered macrocyclic alkynes, which incorporate ortho-aryl, cyclopropane, and cyclopropene units, in good to excellent yields under mild reaction conditions. (Figure presented.).

Full text of DOI:10.1002/adsc.202000360

Title: Dirhodium(II)-Catalyzed Cyclopropanation of Alkyne-Containing
α-Diazoacetates for the Synthesis of Cycloalkynes
Authors: Xinfang Xu, Qian Zeng, Ciwang He, Su Zhou, Kuiyong Dong,
and Lihua Qiu
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000360
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10.1002/adsc.202000360
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.202((will be filled in by the editorial staff))
Dirhodium(II)-Catalyzed Cyclopropanation of Alkyne-
Containing α-Diazoacetates for the Synthesis of Cycloalkynes
Qian Zeng,a Ciwang He,a Su Zhou,b Kuiyong Dong,a Lihua Qiu,a,* and Xinfang Xua,b,*
a
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
Email: qiulihua@suda.edu.cn
b
Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen
University, Guangzhou 510006, China
Email: xuxinfang@mail.sysu.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))
Abstract.
macrocyclization
An
efficient
reaction
dirhodium(II)-catalyzed
of alkyne-containing
diazoacetates through intramolecular metal carbene
cyclopropanation is described. This method provides a
variety of 12- to 22-membered macrocyclic alkynes, which
incorporate ortho-aryl, cyclopropane, and cyclopropene
units, in good to excellent yields under mild reaction
conditions.
Keywords: Diazo compounds; Metal carbenes;
Macrocyclization; Cyclopropanation; Macrocyclic alkyne
Diazo compounds, pervasively used as carbene
precursors, are versatile reagents in modern synthetic
organic chemistry.[1] Although transition-metal-
catalyzed transformations of diazo compounds allow
rapid and efficient assembly of complex molecules
and are widely reported,[2] relevant catalytic carbene
reactions for the direct construction of macrocyclic
rings have received limited attention.[3-7] The seminal
work in this content using intramolecular catalytic
cyclopropanation reaction for the direct synthesis of
macrocyclic molecules has been reported by
Doyle,[3a,3b] and later by Charette (Scheme 1a).[3c]
Doyle’s group generalized this method for the
efficient construction of a variety of macrocyclic
compounds through intramolecular metal carbene
reactions, including cyclopropenation (Scheme 1a),[4]
the Buchner reaction (Scheme 1b),[5] formal coupling
reactions (Scheme 1c),[6] and others.[7] Despite these
achievements, metal carbene reactions have not been
documented for the synthesis of macrocyclic alkynes,
which may be due to their inherent ring strain as well
as the side reaction of metal carbene with alkyne
species.[4] Recently, our group have enabled divergent
access for the straightforward synthesis of
Scheme 1. Macrocycle formation via metal carbene
reactions.
cycloalkynes through copper-catalyzed C(sp2)-H
functionalization and rhodium-prompted Buchner
reaction (Scheme 1d).[8] Due to longstanding research
interest in the construction of privileged cycloalkynes,
the development of efficient and practical synthetic
routes to access cycloalkynes with broad functional
group compatibility and structural diversity is highly
desirable.[9]
1
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10.1002/adsc.202000360
Advanced Synthesis & Catalysis
Over the past few decades, cycloalkynes have
Table 1. Optimization of the reaction conditions.a)
attracted considerable attention from chemists
because of their unique structures that are prevalent
in natural products,[10,11] bioactive molecules,[12] and
materials.[13] Thus, a variety of catalytic strategies for
the construction of macrocyclic alkynes have been
disclosed, such as the palladium-promoted Heck
reaction,[14] the copper-catalyzed Castro-Stephenes
coupling reaction,[15] ring-closing alkyne metathesis
(RCAM),[16] the Nicholas reaction[17,18] and its
analogous version.[19] Recently, gold-catalyzed
coupling has been reported by the Shi group for the
effective construction of cyclic conjugated diynes.[20]
In some cases, reductive elimination of cyclic
haloalkenes has been applied as an alternative
approach for the oriented preparation of alkyne
species.[21] Encouraged by these advances and our
ongoing interest in the exploration of catalytic
carbene chemistry,[8,22] we envisioned that direct
intramolecular cyclopropanation of alkyne embedded
diazoacetate 1 would occur with the tethered alkene
species (R = alkenyl) by avoiding steric strain in the
cyclic transition states. Although the carbene/alkyne
metathesis (CAM) process of the alkyne motif is
kinetically favorable via 5- or 6-membered cyclic
transition states,[23] the alkene species is more
nucleophilic compared to the alkyne species.
Moreover, by introducing an ortho-disubstituted
benzene unit to bend the linear architecture, which
will increase the probability of the reaction happening
between these two reacting species, other
intermolecular side reactions, such as end-to-end
cyclization, or dimerization could be avoided. Herein,
we report an efficient dirhodium(II)-catalyzed
macrocyclization reaction of alkyne-containing
diazoacetates 1 through intramolecular metal carbene
cyclopropanation. This method provides a variety of
12- to 22-membered macrocyclic alkynes, which
Entry Cat (x mol %)
Yields (%)b)2a/3a
Rh2(OAc)4 (1.0)
Rh2(esp)2 (1.0)
Cu(hfacac)2 (5.0)
Cu(OTf)2 (5.0)
[PdCl(ƞ3-C3H5)]2 (5.0)
Rh2(esp)2 (1.0)
Rh2(esp)2 (1.0)
Rh2(esp)2 (1.0)
Rh2(esp)2 (1.0)
Rh2(esp)2 (1.0)
1
2
3
4
5
80/<5
91/<5
46/37
35/30
<5/85
61/<5
89/<5
91/<5
93/<5
88/<5
6c)
7d)
8e)
9f)
10g)
a)
The reactions were carried out on a 0.2 mmol scale: to
the mixture of corresponding catalyst, and 4 Å MS (100
mg) in DCE (2.0 mL), was added 1a (54.0 mg, 0.2 mmol)
in DCE (2.0 mL) via syringe pump over 4 h under argon
o
b)
c)
atmosphere at 20 C. Isolated yields. The reaction was
carried out in one-pot. d) 1a was added via syringe pump in
e)
1.0 h. 1a was added via syringe pump over 6.0 h. f) The
reaction was carried out in one-pot in 20 mL DCM. g) The
reaction was carried out in one-pot in 40 mL DCM.
was obtained only in moderate yields contaminated
with dimerization by-product 3a in almost the same
amounts (entries 3 and 4), whereas the use of
[PdCl(ƞ3-C3H5)]2 only led to by-product 3a in 85%
yield (entry 5). With Rh2(esp)2 as the catalyst, either
in one-pot or by slow addition of 1a, the by-product
3a was not formed (entries 6-10). Comparable
excellent yields were obtained by slowly adding the
diazo compounds in 1 or 6 hours (entries 7 and 8) or
in one-pot under diluted conditions (entries 9 and 10).
Considering the cost of the solvent, slowly addition
of the diazo compound was used (entry 2). We also
investigated asymmetric catalysis for this reaction;
although high yields were obtained when the
reactions were catalyzed by chiral dirhodium
catalysts, their ee values were very low (see Table S1
in SI for details, 3%~6% ee).
With the optimized reaction conditions in hand, the
applicability of the protocol was extended to a variety
of alkyne-containing diazoacetates 1 (Scheme 2).
Both fluoro- and chloro- substituted phenyl on 1
could tolerate the reaction conditions, and the
products 2b and 2c were generated as single
diastereomers in 76% and 75% yields, respectively.
Substrates with cyclohexyl or methyl substitutions on
the methylene linkage did not affect the reaction
profile, delivering the corresponding products 2d and
2e both in high yields, and two isomers were formed
in the latter case. The
incorporate
ortho-aryl,
cyclopropane,
and
cyclopropene units, in good to excellent yields under
mild reaction conditions (Scheme 1e).
The initial exploration was carried out with
diazoacetate 1a as the model substrate in
dichloroethane (DCE) at 20 oC in the presence of 4 Å
molecular sieve, which has shown a promising effect
for the inhibition of the side reaction(s) in our
previous study (Table 1).[8] We investigated a range
of metal catalysts, including dirhodium, copper, and
palladium complexes. Gratifyingly, all of them
promote the reaction smoothly when 1a is added
slowly via syringe pump over 4 h under an argon
atmosphere (entries 1-5), among which the dirhodium
catalysts, both Rh2(OAc)
Rh (esp) , proved to be
4 and
2 2
the better choices for this intramolecular
cyclopropanation, providing macrocyclic alkyne 2a
as the only isolated product in 80% and 91% yields,
respectively (entries 1 and 2). In the reported
literature, both Cu- and Pd-catalysts have shown
obvious advantages in metal carbene coupling
reactions in comparison with the dirhodium
catalysts.[24] In our case, the copper catalysts showed
good catalytic activities, and the desired product 2a
2
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10.1002/adsc.202000360
Advanced Synthesis & Catalysis
Moreover, disubstituted alkenes, including those with
bromo-, aryl, naphthyl, and ester substituents,
provided the corresponding products in 50%-86%
yields with excellent stereoselectivities (2g-2l).
Notably, cyclopropenation with the diazoacetate that
is tethered with a terminal alkyne occurred smoothly
under these conditions, forming cycloalkyne 2m that
incorporates a cyclopropene unit in 85% yield.
Subsequently, we surveyed these linear materials
with different chain lengths, finding that macrocyclic
alkynes with ring sizes from 14 to 22 were obtained
in
58%-89%
yields
with
moderate
diastereoselectivities (2n-2t). The stereochemistry of
these products was determined by NOE analysis (see
Figure S1-4 in SI for details). Moreover, the amide-
containing product 2u and 12-membered cycloalkyne
2v were isolated as single isomer in 78% and 86%
yields, respectively. The structure of 2g was
confirmed by single-crystal X-ray diffraction
analysis.[25]
To demonstrate the utility of current method, we
performed the reaction on a gram scale (eq 1, 5.1
mmol) to provide 1.146 g pure 2g in 70% yield. It
should be mentioned that the easily transformable
bromide survived under the current reaction
conditions. Further applications in the construction of
macrocyclic alkynes with structural diversity and
broad functional group compatibility is envisioned.
In summary, we have developed an efficient
dirhodium(II)-catalyzed macrocyclization of alkyne-
containing diazoacetates through intramolecular
metal carbene cyclopropanation, which provides
a
straightforward and practical access to a variety of
12- to 22-membered macrocyclic alkynes in good to
excellent yields. The salient features of this
reaction include mild conditions, amenable to the
gram scale, good functional group tolerance, and
providing unique cycloalkynes that incorporate
ortho-aryl, cyclopropane, and cyclopropene units.
Further applications of this method for the direct and
effective construction of appealing macrocyclic
frameworks with structural diversity could be
envisioned.
Scheme 2. Substrate scope of cycloalkynes. The reactions
were carried out on a 0.2 mmol scale: to the mixture of
Rh2(esp)2 (1.5 mg, 1.0 mol%), and 4 Å MS (100 mg) in
DCE (2.0 mL), was added a solution of diazo compound 1
(0.2 mmol) in DCE (2.0 mL) via syringe pump over 4 h
under argon atmosphere at 20 ℃, and the reaction was
stirred for additional 1 h under these conditions. The yields
are given in isolated yields.
Experimental Section
General Procedure for the Cyclopropanation Reaction
(Scheme 2): To a 10-mL oven-dried vial containing a
magnetic stirring bar, Rh2(esp)2 (1.5 mg, 1.0 mol%), and
4Å MS (100 mg) in DCE (2.0 mL), diazo compound 1 (0.2
mmol) in DCE (2.0 mL) was added via a syringe pump
over 4 h under argon atmosphere at 20 ℃. After addition,
the reaction mixture was stirred under these conditions
until consumption of the material was complete (monitored
by TLC, about 1 hour). Then the reaction mixture was
trisubstituted alkene species worked well and
provided 2f in 84% yield with two diastereomers.
3
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10.1002/adsc.202000360
Advanced Synthesis & Catalysis
purified by column chromatography on silica gel without
any additional treatment (hexanes : EtOAc = 15:1 to 10:1)
to give the pure products 2 in moderate to high yields.
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Acknowledgements
Support for this research from the National Natural Science
Foundation of China (21971262), Guangdong Provincial Key
Laboratory of Chiral Molecule and Drug Discovery
(2019B030301005), and The Program for Guangdong
Introducing Innovative and Entrepreneurial Teams (No.
2016ZT06Y337) is greatly acknowledged. We also thank Prof. M.
P. Doyle from UTSA for proofreading the manuscript.
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crystallographic data for 2g in this paper. These data
can be obtained free of charge from The Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
5
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10.1002/adsc.202000360
Advanced Synthesis & Catalysis
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