Convenient access to pyrrolidin-3-ylphosphonic acids and tetrahydro-2H-pyran-3-ylphosphonates with multiple contiguous stereocenters from nonracemic adducts of a Ni(II)-catalyzed Michael reaction

Article abstract of DOI:10.3762/BJOC.16.174

A new synthetic strategy toward nonracemic phosphoryl-substituted pyrrolidines and tetrahydropyranes with three and five contiguous stereocenters is presented. Readily available β-keto phosphonates react with conjugated nitroolefins in the presence of a c

Full text of DOI:10.3762/BJOC.16.174

Convenient access to pyrrolidin-3-ylphosphonic acids and
tetrahydro-2H-pyran-3-ylphosphonates with multiple
contiguous stereocenters from nonracemic adducts
of a Ni(II)-catalyzed Michael reaction
Alexander N. Reznikov*1, Dmitry S. Nikerov1, Anastasiya E. Sibiryakova1,
Victor B. Rybakov2, Evgeniy V. Golovin1 and Yuri N. Klimochkin1
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2020, 16, 2073–2079.
1Department of Organic Chemistry, Samara State Technical
University, Molodogvardeyskaya str., 244, 443100 Samara, Russian
Federation and 2Department of Chemistry, Moscow State University,
Leninskie Gory, 1, 119991, Mosсow, Russian Federation
https://doi.org/10.3762/bjoc.16.174
Received: 15 May 2020
Accepted: 10 August 2020
Published: 25 August 2020
Email:
Alexander N. Reznikov* - reznikov.an@samgtu.ru
Associate Editor: K. Grela
* Corresponding author
© 2020 Reznikov et al.; licensee Beilstein-Institut.
License and terms: see end of document.
Keywords:
asymmetric catalysis; Michael addition; phosphonates; pyrrolidines;
tetrahydropyranes
Abstract
A new synthetic strategy toward nonracemic phosphoryl-substituted pyrrolidines and tetrahydropyranes with three and five
contiguous stereocenters is presented. Readily available β-keto phosphonates react with conjugated nitroolefins in the presence of a
chiral Ni(II) complex to give nitro keto phosphonates with two stereocenters with excellent enantioselectivity and moderate to high
diastereoselectivity. These products were used for a reductive cyclization leading to pyrrolidin-3-ylphosphonic acid and for reac-
tions with aldehydes yielding tetrahydropyranylphosphonates as individual stereoisomers. These nonracemic heterocycles contain-
ing phosphoryl moieties are useful for designing new pharmacologically active compounds.
Introduction
Сhiral phosphonates [1,2] and phosphoryl-substituted hetero- Oxygen-containing heterocycles containing a phosphoryl group
cycles [2-4] have received significant attention in recent years are also of interest in the development of new drugs. It is known
due to their wide range of biological activity. For example, that phosphorylated carbohydrate analogues 4 and 5 are
SF-2312 (1) is a natural antibiotic – an enolase inhibitor neuraminidase inhibitors (Figure 1) [8,9].
produced by the actinomycete Micromonospora [5]. Dipeptide
analogs with phosphonoproline 2 and piperidine-2-phosphonic These circumstances create an interest in discovering synthetic
acid 3 are potent inhibitors of dipeptidyl peptidase IV [6,7]. routes for obtaining nonracemic phosphoryl-substituted hetero-
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Beilstein J. Org. Chem. 2020, 16, 2073–2079.
substituted heterocycles. The present work reports on the syn-
thesis of nonracemic phosphoryl-substituted pyrrolidines and
tetrahydropyranes via Ni(II)-catalyzed asymmetric Michael ad-
dition of β-keto phosphonates to conjugated nitroolefins.
Results and Discussion
For the synthesis of nonracemic polysubstituted pyrrolidin-3-
ylphosphonic acids and tetrahydropyranylphosphonates, we
assumed that the 4-nitro-2-oxophosphonates – the Michael
adducts of β-keto phosphonates and nitroolefins – are suitable
precursors, considering that the Ni(II)-catalyzed Michael addi-
tion was carried out not only enantioselectively, but also dia-
stereoselectively, such has been previously described [45].
These considerations prompted us to explore further applica-
tions of 4-nitro-2-oxophosphonates containing two contiguous
stereocenters for the synthesis of the target compounds.
Initially, 4-nitro-2-oxophosphonates 6a–f (Figure 2) were syn-
thesized similar to the reported procedure [45,46] from corre-
sponding β-keto phosphonates and nitroolefins in the presence
of 2 mol % of the Ni(II) complex with dr 11:1 to 1:0 and
98 –> 99% ee (see Supporting Information File 1).
Figure 1: Pharmacologically active nonracemic phosphonates with
heterocyclic moieties.
cycles. Thus, in recent years, effective methods for the asym-
metric synthesis of chiral phosphonates containing octahydroin-
dole [10], tetrahydroquinoline [11], tetrahydroisoquinoline
[11,12], β-carboline [13], morpholine [14], and isoindoline [15]
moieties have been developed. Obtained in an enantiomerically
pure form, phosphonoproline and its analogues [16-19] were
among the first compounds in this series. Surprisingly, the
methods for obtaining chiral pyrrolidin-3-ylphosphonic acids,
tetrahydropyranylphosphonic acids and their esters have experi-
enced minimal development [20-22]. The use of atom-efficient
methods of asymmetric catalysis for the synthesis of such com-
pounds is extremely relevant. The chiral metal-complexes-cata-
lyzed [23-26] or organocatalyzed [27-32] Michael reaction is
one of the most important synthetic tools for the asymmetric
formation of a C–C bond. Moreover, the generation of the first
stereocenter of a given configuration during the catalytic
process leads to the possibility of creating enantiomerically pure
compounds with several stereocenters through the directed
regulation of diastereoselectivity in subsequent transformations,
which can be realized as stepwise or cascade processes. Due to
this reason, the Michael reaction was successfully used over the
last decade to synthesize a wide range of heterocycles [33-44].
2-Oxo-4-nitrophosphonates [45,46], the Michael adducts of
β-keto phosphonates and nitroolefins, can be considered as
versatile reagents for the synthesis of various phosphoryl-
Figure 2: Starting nonracemic 4-nitro-2-oxophosphonates.
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Beilstein J. Org. Chem. 2020, 16, 2073–2079.
A search for acceptable hydrogenation conditions was carried An X-ray diffraction study [50] of the formyl derivative 10a
out using compound 6a. Hydrogenation in the presence of showed its (2R,3R,4S)-configuration (Figure 3). The absolute
Raney nickel or Pd/C in various solvents leads to a mixture of configuration of the other phosphonates 10b–d and 11b–d is
products, among which 8 and 9 are identified (Scheme 1).
assumed by analogy.
A satisfactory yield of the desired product 7 (78% by 31P NMR
of reaction mixture) was achieved when the hydrogenation was
carried out in acetic acid in the presence of Pd/C. However,
phosphonate 7 was unstable: already during its isolation, it was
partially transformed into compounds 8 and 9. It can be
assumed that N-alkylation by the phosphoryl group occurs [47-
49].
To avoid this undesirable process, the product 7 was formy-
lated before its isolation. The formylated product 10a may be
purified by chromatography without decomposition. Subse-
quent acid hydrolysis of compound 10a leads to pyrro-
lidinylphosphonic acid hydrochloride 11a (Scheme 2).
Similarly, pyrrolidinylphosphonic acids 11b–d were obtained
from the corresponding phosphonates 6b,c,e (Scheme 2).
Figure 3: ORTEP diagram of (2R,3R,4S)-10a.
Scheme 1: Intermolecular N-methylation of reduction product 7.
Scheme 2: Synthesis of pyrrolidinyl phosphonic acids 11a–d.
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Beilstein J. Org. Chem. 2020, 16, 2073–2079.
Hydrogenation of phosphonates 6d,f with o-anisyl and bulky reaction was carried out in an aqueous–organic medium. Fortu-
adamantan-1-yl substituents at the carbonyl leads to a mixture nately, an individual diastereomer of Henry/acetalyzation prod-
of unidentified products.
uct 13a was obtained when K2CO3 in combination with
TEBAC was used as a catalyst. A THF/water ratio of 7.5:1 is
At the next stage of this work, the Henry/acetalization reaction important in order to get the best yield (Table 1, entry 9). Lower
with phosphonate 6e was studied. To optimize the reaction yields and dr values for compound 13a were obtained when
conditions various bases and solvents were used. The reaction 18-crown-6 was used as the phase-transfer catalyst (Table 1,
of phosphonate 6e with propionic aldehyde 12a was used as a entries 10–12).
model reaction (see Table 1).
With the optimized reaction conditions in hand, the transformat-
Initially, the catalytic ability of organic bases was studied for ion was studied with a series of phosphonates and aldehydes.
the Henry/acetalyzation reaction by using 0.1–1.0 equiv of cata- As shown in Scheme 3, the reaction of phosphonate 6e gave
lyst in THF as a solvent. Unfortunately, no product formation moderate yields with various aliphatic and aromatic aldehydes
was observed in the presence of N,N-dimethylaniline (Table 1, 12a–f. The presence of a bulkier (compared to methyl) group at
entry 1) and unidentified products were formed when stronger the carbonyl in the phosphonates 6a–d,f leads to no reaction.
bases such as triethylamine or DBU were used (Table 1, entries
2 and 3). Later on, inorganic bases in combination with a phase Tetrahydropyranols 13a–f were obtained with good diastereo-
transfer agent such as benzyltriethylammonium chloride meric purity. In the 1H NMR spectra of 13a–f signals of
(TEBAC) were tried as catalysts for the same reaction. Simi- methine groups with characteristic spin–spin coupling con-
larly, no products were detected in the reaction even after 72 h stants for axially located protons (12.1, 12.3 and 12.5 Hz) were
in the presence of 1 equiv of potassium phosphate or carbonate observed.
with TEBAC (0.1 equiv, Table 1, entries 4 and 5). If potassium
fluoride or cesium carbonate were used as a base, the initial The structure and absolute (2S,3R,4S,5S,6R)-configuration of
phosphonate 6e was consumed in a few hours, but unidentified the tetrahydropyranol 13b have been confirmed by single-
products were formed (Table 1, entries 6 and 7). After this, the crystal X-ray crystallographic analysis (Figure 4) [51].
Table 1: Optimization of the conditions of Henry/acetalyzation reaction with phosphonate 6ea.
Entry
Base
Phase transfer catalyst
Solvent
Yield of 13a (%)
drb
1
PhNMe2
Et3N
–
THF
0
–
2
–
THF
0c
0c
0
–
3
DBU
–
THF
–
4
K3PO4
K2CO3
KF
TEBAC
TEBAC
TEBAC
–
THF
–
5
THF
0
–
6
THF
0c
0c
0c
34
30
17
12
–
7
Cs2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
THF
–
8
TEBAC
TEBAC
18-crown-6
18-crown-6
18-crown-6
THF/H2O 1:1
THF/H2O 7.5:1
CH3CN
THF
–
9
1:0
11:1
16:1
10:1
10
11
12
CH2Cl2
aReaction conditions: phosphonate 6e (1.58 mmol), aldehyde 12a (15.8 mmol), solvent (17 mL), base (1.58 mmol), phase transfer catalyst
(0.158 mmol), rt, 72 h; bdetermined by 31P NMR; cfull phosphonate 6e conversion was observed and unidentified products were formed.
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Beilstein J. Org. Chem. 2020, 16, 2073–2079.
Scheme 3: Synthesis of tetrahydropyranylphosphonates 13a–f via diastereoselective Henry/acetalyzation reaction.
Dehydration of compound 13b in the presence of p-toluene-
sulfonic acid gives dihydropyran 14 as a single stereoisomer
(Scheme 4).
Scheme 4: Synthesis of (3,4-dihydro-2H-pyran-5-yl)phosphonate 14.
Conclusion
In summary, a convenient protocol for the synthesis of phos-
phoryl-substituted pyrrolidines with three contiguous stereo-
centers via asymmetric addition of β-keto phosphonates to
nitroolefins and subsequent reductive cyclization of enantio-
enriched, diastereomerically pure Michael adducts was de-
veloped. The present study also demonstrates that the diastereo-
Figure 4: ORTEP diagram of (2S,3R,4S,5S,6R)-13b.
All hydrogen atoms and the hydroxy group occupy an axial po- selective cascade Henry/acetalyzation reaction with keto nitro
sition, while the remaining substituents are in equatorial posi- phosphonates and aldehydes leading to tetrahydropyranylphos-
tions. This is consistent with the 1H NMR data for other similar phonates can be efficiently performed within an aqueous-
tetrahydropyranols 13b–f, therefore, their configuration was organic medium with K2CO3/TEBAC as the catalyst, and the
assumed by analogy.
corresponding products can be obtained with high diastereo-
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Beilstein J. Org. Chem. 2020, 16, 2073–2079.
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Supporting Information
Supporting Information File 1
Experimental procedures, copies of NMR, FTIR, and mass
spectra, HPLC and X-ray diffraction data.
[https://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-16-174-S1.pdf]
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Crystallographic information files (CIF).
[https://www.beilstein-journals.org/bjoc/content/
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The authors gratefully acknowledge the support of this work by
the Russian Science Foundation (project 18-13-00447). Spec-
tral and chromatographic analysis was performed by joint use
center «Research of physical and chemical properties of
substances and materials» with financial support of the Russian
Ministry of Science and Higher Education for a basic part of a
research project 0778-2020-0005. The X-ray studies were per-
formed in the frame of the development program of the
Moscow State University.
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ORCID® iDs
Chem. Heterocycl. Compd. 2016, 52, 503–506.
Alexander N. Reznikov - https://orcid.org/0000-0002-6056-6415
Dmitry S. Nikerov - https://orcid.org/0000-0002-1603-6185
Anastasiya E. Sibiryakova - https://orcid.org/0000-0001-5005-1373
Victor B. Rybakov - https://orcid.org/0000-0002-6720-0619
Evgeniy V. Golovin - https://orcid.org/0000-0003-4008-8433
Yuri N. Klimochkin - https://orcid.org/0000-0002-7335-4040
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