Chiral Bidentate Phosphoramidite-Pd Catalyzed Asymmetric Decarboxylative Dipolar Cycloaddition for Multistereogenic Tetrahydrofurans with Cyclic N-Sulfonyl Ketimine Moieties

Article abstract of DOI:10.1021/acs.orglett.1c01411

An asymmetric [3 + 2] cycloaddition of vinyl ethylenecarbonates (VECs) and (E)-3-arylvinyl substituted benzo[d] isothiazole 1,1-dioxides has been developed using the Pd complex of a bidentate phosphoramidite (Me-BIPAM) as the catalyst, providing a wide variety of chiral multistereogenic vinyltetrahydrofurans in good yields with excellent diastereo- and enantioselectivities (up to >20:1 dr, 99% ee).

Full text of DOI:10.1021/acs.orglett.1c01411

pubs.acs.org/OrgLett
Letter
Chiral Bidentate Phosphoramidite-Pd Catalyzed Asymmetric
Decarboxylative Dipolar Cycloaddition for Multistereogenic
Tetrahydrofurans with Cyclic N‑Sulfonyl Ketimine Moieties
Hao-Peng Lv, Xiao-Peng Yang, Bai-Lin Wang, Hao-Di Yang, Xing-Wang Wang,* and Zheng Wang*
Cite This: Org. Lett. 2021, 23, 4715−4720
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ABSTRACT: An asymmetric [3 + 2] cycloaddition of vinyl ethyl-
enecarbonates (VECs) and (E)-3-arylvinyl substituted benzo[d] isothia-
zole 1,1-dioxides has been developed using the Pd complex of a bidentate
phosphoramidite (Me-BIPAM) as the catalyst, providing a wide variety of
chiral multistereogenic vinyltetrahydrofurans in good yields with excellent
diastereo- and enantioselectivities (up to >20:1 dr, 99% ee).
etrahydrofuran derivatives and cyclic N-sulfonyl imines
to develop a synthetic route for efficient construction of target
compounds bearing both motifs and multistereogenic centers
within a single molecular skeleton and, most preferably, in a
stereochemically well-controlled manner.
T
are useful synthetic building blocks and widely present as
structural motifs in natural products1 and pharmaceutical
ingredients with a spectrum of biological activities.2,3 As
exemplified in Figure 1, agastinol is an inhibitor of apoptosis,2a
In this context, catalytic asymmetric cycloaddition reactions,
particularly the asymmetric [3 + 2] cycloaddition catalyzed by
various transition metals, have been demonstrated to be highly
efficient for access to diverse multistereogenic tetrahydrofuran
derivatives.10 In 1979, the Trost and Chan group reported the
first cycloaddition of π-allyl-palladium intermediates with
olefins bearing electron-withdrawing groups, which provided
[3 + 2] cycloaddition products of cyclopentanes with exocyclic
methylene moieties.11 Since then, extensive research work has
been reported for the construction of diverse cyclic structures
by means of zwitterionic allylpalladium intermediates.12
Notably, vinylethylene carbonates (VECs) as a type of
zwitterionic allylpalladium precursor are more stable and
readily accessible than the traditional butadiene oxide and
isoprene oxide.13 The zwitterionic allylpalladium intermediates
from VECs can undergo the asymmertirc cycloaddition process
with diverse substrates including aldehydes,14 imines,15
isothiocyanates,16 and methyleneindolinones alkenes17 with
impressive outcomes. Just recently, Kim and co-workers
reported Pd-catalyzed asymmetric [3 + 2] and [5 + 2]
cycloadditions of sulfamate-derived cyclic imines and VECs in
Figure 1. Selective bioactive molecules.
and lasalocid A is an antibacterial agent.2b Sesaminone, isolated
from a culture of Streptomyces sp. IT-44, displays micromolar
activity against Enterococcus faecium.2c Amphidinolide X shows
promising cytotoxicity against murine lymphoma and human
epidermoid carcinoma.2d Finally, the two benzo[d]isothiazole
1,1-dioxides shown in Figure 1 are a potential NS5b inhibitor
of HCV (hepatitis C virus)3a and kinase inhibitor,3b
respectively. Over the past several decades, a variety of
synthetic methods, including the Prins cyclization,4 ring-
closing olefin metathesis,5 oxidative cyclization of alkenes,6
electrophilic cyclization of unsaturated alcohols,7 single or
cascade cyclization of 1,4-diols or polyepoxides,8 and so on,9
have been developed to construct multisubstituted tetrahy-
drofuran molecules. Given the salient pharmacological profiles
of both tetrahydrofuran derivatives and cyclic N-sulfonyl imine
analogues, it would be highly desirable for medicinal research
Received: April 28, 2021
Published: June 7, 2021
https://doi.org/10.1021/acs.orglett.1c01411
© 2021 American Chemical Society
Org. Lett. 2021, 23, 4715−4720
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a
the presence of a phosphoramidite ligand or a diphosphine
ligand, respectively (Scheme 1a).18 Based on the previous
Table 1. Optimization of the Reaction Conditions
Scheme 1. Asymmertic Cycloaddition of VECs with Cyclic
Imines
b
c
d
Entry
Ligand
Solvent
Yield (%)
dr
ee (%)
1
2
3
4
5
6
7
8
L1
L2
L3
L4
L5
L6
L7
L8
L9
L10
L9
L9
L9
L9
L9
L9
L9
L9
L9
L9
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
THF
NR
43
35
10
38
56
50
45
53
33
67
60
58
NR
63
51
70
71
52
75
−
−
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
10:1
70
23
44
6
79
74
25
92
36
98
97
97
−
97
98
80
99
99
99
advances in cycloaddition reaction of VECs with cyclic
sulfamidate imines, we proposed the asymmetric cycloaddition
of VECs with (E)-3-arylvinyl substituted benzo[d]isothiazole
1,1-dioxides, readily derived from saccharins, may provide a
new route for the construction of enantiomerically enriched
multistereogenic tetrahydrofuran derivatives bearing a cyclic
N-sulfonyl imine moiety. We envisioned that, in the presence
of a palladium catalyst, the zwitterionic π-allyl-Pd intermediate
I would be generated from VECs 1 by CO2 extrusion, and then
the oxygen anion may react with the electrophilic CC or
CN double bond of the electron-deficient 1-azadiene moiety
of 2. Further intramolecular attack of the resulting C- or N-
centered nucleophile on the π-allyl intermediate would lead to
either [3 + 2] or [3 + 4] cycloaddition products, respectively,
with the regioselectivity being controlled by the stereo-
electronic nature of both the reactant and the chiral ligand
(Scheme 1b). Herein, we present the results of using the chiral
bidentate phosphoramidite19 of Me-BIPAM for palladium
catalyzed asymmetric [3 + 2] cycloaddition of VECs 1 and
saccharin-derived cyclic imines bearing a vinylarene substituent
2, providing an array of multistereogenic tetrahydrofuran
derivatives bearing a cyclic N-sulfonyl imine moiety in good
yields and excellent stereoselectivities.
We commenced the study by screening reaction parameters
for Pd-catalyzed asymmetric cycloaddition of VECs 1a and
(E)-3-styrylbenzo[d]isothiazole 1,1-dioxide 2a. The reactions
were typically conducted using 5 mol % of Pd2(dba)3 and 12
mol % of a chiral ligand as the catalyst, and the results were
summarized in Table 1. Several different types of chiral
phosphorus-containing ligands were first examined in the
reaction performed in toluene at 35 °C (entries 1−10).
Whereas no reaction occurred in the presence of diphosphine
ligand L1 (entry 1), the reactions using phosphorus-oxazoline
L2, monodentate phosphoramidites ligands L3−8, or O-
tethered bidentate phosphoramidites L9 and L10 led to only
the [3 + 2] cycloadduct 3aa as the isolated product, albeit with
remarkably varied enantioselectivities in each case (entries 2−
10). By the use of bidentate phosphoramidite ligand of L9, the
desired product 3aa was delivered in 53% yield with >20:1 dr
and 92% ee (entry 9). Apart from toluene, several other types
9
10
11
12
13
14
15
16
17
18
19
DCM
MeCN
MeOH
MTBE
THF
THF
THF
−
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
e
f
g
h
THF
THF
i
20
a
Unless otherwise noted, reactions were carried out with 1a (0.10
mmol), 2a (0.10 mmol), Pd2(dba)3 (5 mol %) and L (12 mol %) in
b
solvent (1.0 mL) at 35 °C by an oil bath for 15 h. Isolated yields.
c
d
e
Determined by 1H NMR analysis. Determined by chiral HPLC. 20
f
g
h
°C. 40 °C. L9 (15 mol %). Pd2(dba)3 (2.5 mol %) and L9 (7.5 mol
%). 2a (0.15 mmol), L9 (15 mol %).
i
of common organic solvents were also evaluated (entries 11−
15), among which THF was determined to be optimal for the
reaction, affording the desired product 3aa in 67% yield with
>20:1 dr and 98% ee (entry 11). Subsequently, the reaction
conditions were further optimized by examination of the
effects of reaction temperature and catalyst loadings. It was
found that 35 °C was still optimal for this reaction; elevating or
lowering the reaction temperature led to a decline in ee or
yield of 3aa (entry 11 vs entries 16 and 17). Meanwhile, by
increasing the loading of L9 to 15.0 mol %, the corresponding
reaction provided the product 3aa in 71% yield with 99% ee
and >20:1 dr (entry 18). However, when the catalyst loadings
were reduced to half, the yield of 3aa was decreased to 52%,
albeit both the dr and ee values remained unchanged (entry
19). Finally, the optimized conditions were established as the
reaction being performed with a 1:1.5 molar ratio of 1a to 2a,
in the presence of 5.0 mol % of Pd2(dba)3 and 15.0 mol % of
the ligand L9 in THF at 35 °C (entry 20; see SI for more
details).
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Under the optimal conditions, the generality of the Me-
BIPAM/Pd-catalyzed asymmetric cycloaddition reaction was
evaluated. As summarized in Scheme 2, various VECs (1b−1t)
to be compatible for this transformation, affording the
corresponding product 3rb−3tb in 57−73% yields with
17:1−>20:1 dr and 94−98% ee values, respectively. Notably,
the absolute configuration of 3lb was unambiguously
established as (2S,3R,4R) by X-ray crystallographic analysis,
while those of the other products were assigned by analogy
(see SI).
a
Scheme 2. Substrate Scope
We have further explored the substrate scope of (E)-3-
arylvinyl substituted benzo[d]isothiazole 1,1-dioxides 2a−p,
with different aromatic substituents on the carbon−carbon
double bonds, in their reactions with VEC compound 1a,
respectively (Scheme 3). The substrates 2a, 2c, and 2d with a
a
Scheme 3. Substrate Scope
a
Unless otherwise noted, reaction conditions as for entry 20 in Table
1.
bearing diverse aryl groups were well-tolerated in the reactions
with 2b, and the corresponding multistereogenic tetrahydro-
furan derivatives 3ab−3tb were obtained in moderate to good
yields (55−73%) with generally excellent diastereo- and
enantioselectivities (>20:1 dr, 94−99% ee). For the substrates
1b−1g with an electron-donating (−Me, −OMe) or electron-
withdrawing (−F, −Cl, −Br, −CF3) group on the para-
position of the substrate phenyl ring, the desired products
3bb−3gb were isolated in 57−73% yields with >20:1 dr and
96−99% ee values, respectively. For substrates 1h−1k with an
electron-withdrawing (−F, −Br) or electron-donating (−OMe,
−Ph) group on the meta-position of the substrate phenyl ring,
the reactions also afforded the desired products 3hb−3kb in
62−73% yields with >20:1 dr and 98−99% ee. The substrates
1l−1n containing a −OMe, −F, or −Cl substituent at the
ortho-position on the phenyl ring were also suitable partners
for this transformation, which furnished the corresponding
products 3lb−3nb in 60−70% yields with 18:1−>20:1 dr and
94−99% ee values, respectively. In addition, for reactions
involving substrates 1o−1q with two groups (−OMe, −F, or
−Cl) substituted at the substrate phenyl rings, the correspond-
ing products 3ob−3qb were obtained in 57−72% yields with
13:1−>20:1 dr, 98−99% ee. Finally, the substrates 1r−1t with
a heterocyclic or fused aromatic hydrocarbon were also proven
a
Unless otherwise noted, reaction conditions as for entry 20 in Table
1.
para-OMe, −F, or −Cl on the phenyl ring were first
investigated in this transformation, which provided the desired
products 3aa, 3ac, and 3ad in 64−75% yields with >20:1 dr
and 97−99% ee, respectively. Then, for substrates 2e−2k
bearing an electron-withdrawing group (−F, −Cl, −Br) or an
electron-donating group (−Me, −OMe) at the meta-and ortho-
position of the phenyl ring, the corresponding reactions
afforded the cycloadducts 3ae−3ak in 59−65% yields with 7:1
to >20:1 dr and 91−99% ee values, respectively. For substrate
2l bearing 2,4-dichloro substituents, the catalytic outcomes of
both the enantio- and diastereoselectivity were decreased
dramatically to 17:1 dr and 81% ee. In addition, the reactions
involving in 2m and 2n with a 2-thiophenyl or 2-naphthyl
group proceeded well to afford the cycloadducts 3am and 3an
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Letter
in 65% and 62% yields with >20:1 dr and 99% and 89% ee,
respectively. Unfortunately, reactions involving substrates 2o
and 2p, bearing a strong electron-withdrawing group (−NO2,
−CN), failed to furnish their corresponding cycloadducts. The
solid state structure of 3ae was further determined by single
crystal X-ray diffraction analysis, and its absolute configuration
was thus unambiguously established as (2S,3R,4R) (see SI).
The synthetic application of the present protocol was
demonstrated by the gram-scale transformation and product
derivatization (Scheme 4). The reaction proceeded smoothly
Scheme 4. Scale Up and Derivatization
Figure 2. Plausible schematic models.
In summary, we have developed a Pd catalyzed asymmetric
[3 + 2] cycloaddition of VECs and (E)-3-arylvinyl substituted
benzo[d]isothiazole 1,1-dioxides using a chiral bis-phosphor-
amidite ligand (Me-BIPAM). The reaction protocol features a
broad substrate scope and good functional group tolerance,
affording a wide variety of optically active tetrahydrofuran
derivatives in moderate to good yields with excellent diastereo-
and enantioselectivities. The resultant chiral tetrahydrofuran
derivatives possess three consecutive tertiary and quaternary
stereocenters, bear a biologically significant cyclic N-sulfonyl
ketimine motif, and contain a vinyl group that allows for
further synthetic elaboration.
ASSOCIATED CONTENT
* Supporting Information
■
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.1c01411.
Experimental details, compound characterization, and X-
ray crystallographic data for 3ae and 3lb (PDF)
at 3.50 mmol scale of 1f under the optimized conditions, and
the cycloadduct 3fb was isolated in good yield (1.10 g, 67%)
with >20:1 dr and 98% ee. In a reductive transformation, the
Pd/C catalyzed hydrogenation of the product 3fb afforded the
product 4a in 44% yield with retention of stereochemical
outcomes (>20:1 dr and 98% ee). Subsequently, a cascade
Heck vinylation and arylation of the product 3fb and 2 equiv of
iodobenzene was accomplished in the presence of Pd(OAc)2
with the potassium carbonate at 100 °C in DMF, affording the
double coupling product 4b in 82% yield with >20:1 dr and
99% ee. Finally, palladium catalyzed Suzuki coupling of 3fb
with phenylboronic acid furnished the corresponding product
4c in 76% yield with >20:1 dr and 99% ee.
Accession Codes
CCDC 2040772 and 2055984 contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Authors
■
Based on the experimentally observed major stereoisomers
for the cycloadducts (2S,3R,4R)-3, a stereoselectivity model for
Me-BIPAM-Pd catalyzed [3 + 2] cycloaddition of 1 and 2 was
postulated. As shown in Figure 2, asymmetric oxa-Michael
addition or concerted [3 + 2] cycloaddition would proceed via
transition B, wherein the steric allyl moiety and the BIPAM
ligand are minimized, leading to the formation of (2S,3R,4R)-3
as the major stereoisomer. In contrast, a severe steric clash
would develop between the aryl group (Ar1) in the allyl moiety
and the NMe2 motif of the BIPAM ligand in B′, which is thus
disfavored in the catalysis.
Xing-Wang Wang − Key Laboratory of Organic Synthesis of
Jiangsu Province, College of Chemistry, Chemical Engineering
and Materials Science & Collaborative Innovation Center of
Suzhou Nano Science and Technology, Soochow University,
Suzhou 215123, China; orcid.org/0000-0002-6004-
8458; Email: wangxw@suda.edu.cn
Zheng Wang − State Key Laboratory of Organometallic
Chemistry, Center for Excellence in Molecular Synthesis,
Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, Shanghai 200032, China; Email: wzsioc@
mail.sioc.ac.cn
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Authors
pubs.acs.org/OrgLett
Letter
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Hao-Peng Lv − Key Laboratory of Organic Synthesis of
Jiangsu Province, College of Chemistry, Chemical Engineering
and Materials Science & Collaborative Innovation Center of
Suzhou Nano Science and Technology, Soochow University,
Suzhou 215123, China
Xiao-Peng Yang − Key Laboratory of Organic Synthesis of
Jiangsu Province, College of Chemistry, Chemical Engineering
and Materials Science & Collaborative Innovation Center of
Suzhou Nano Science and Technology, Soochow University,
Suzhou 215123, China
Bai-Lin Wang − Key Laboratory of Organic Synthesis of
Jiangsu Province, College of Chemistry, Chemical Engineering
and Materials Science & Collaborative Innovation Center of
Suzhou Nano Science and Technology, Soochow University,
Suzhou 215123, China
Hao-Di Yang − Key Laboratory of Organic Synthesis of
Jiangsu Province, College of Chemistry, Chemical Engineering
and Materials Science & Collaborative Innovation Center of
Suzhou Nano Science and Technology, Soochow University,
Suzhou 215123, China
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Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.1c01411
Notes
The authors declare no competing financial interest.
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Acetoxymethyl −3-allyltrimethylsilane for Methylenecyclopentane
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ACKNOWLEDGMENTS
■
We are grateful for financial support from the National Natural
Science Foundation of China (21971176, 21772221).
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