A One-Pot Iodo-Cyclization/Transition Metal-Catalyzed Cross-Coupling Sequence: Synthesis of Substituted Oxazolidin-2-ones from N-Boc-allylamines

Article abstract of DOI:10.1021/acs.orglett.0c01114

A one-pot iodo-cyclization/transition metal-catalyzed cross-coupling sequence is reported to access various C5-functionalized oxazolidin-2-ones from unsaturated N-Boc-allylamines. Depending on the Grignard reagents used for the cross-coupling, e.g., aryl- or cyclopropylmagnesium bromide, a cobalt or copper catalyst has to be used to obtain the functionalized oxazolidin-2-ones in good yields.

Full text of DOI:10.1021/acs.orglett.0c01114

pubs.acs.org/OrgLett
Letter
A One-Pot Iodo-Cyclization/Transition Metal-Catalyzed Cross-
Coupling Sequence: Synthesis of Substituted Oxazolidin-2-ones
from N‑Boc-allylamines
Pauline Chaumont-Olive and Janine Cossy*
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ABSTRACT: A one-pot iodo-cyclization/transition metal-cata-
lyzed cross-coupling sequence is reported to access various C5-
functionalized oxazolidin-2-ones from unsaturated N-Boc-allyl-
amines. Depending on the Grignard reagents used for the cross-
coupling, e.g., aryl- or cyclopropylmagnesium bromide, a cobalt or
copper catalyst has to be used to obtain the functionalized
oxazolidin-2-ones in good yields.
xazolidin-2-ones have been widely developed especially
Oas chiral auxiliaries since the development of Evans
aldolization using C4-functionalized oxazolidin-2-ones.1 De-
spite the fact that C5-functionalized oxazolidin-2-ones have
low benefit toward chiral induction, they are of interest as
biologically active compounds. In 1978, E.I. Du Pont de
Nemours and Company reported for the first time their
antibiotic activity,2 and since then, these heterocycles are
highly represented among several bioactive compounds, such
as linezolid and derivatives as antibacterial agents,3 the
antidepressant toloxatone,4 and fenspiride, a bronchodilator.5
In addition, functionalized oxazolidin-2-ones are also present
in alkaloid natural products such as in the stemoxazolidinone
family6 (Figure 1).
Nowadays, the development of methods in organic synthesis
is mainly driven by the use of nontoxic, cheap, and earth-
abundant metals. For example, in cross-couplings, the
replacement of palladium catalysts by metals of the fourth
row of the periodic table, such as Fe, Co, Ni, and Cu, is
favored.9−13 In the context of our studies on cobalt-catalyzed
cross-couplings between alkyl halides and Grignard reagents,14
we report herein a one-pot iodo-cyclization/cross-coupling
sequence to access a diversity of C5-functionalized oxazolidin-
2-ones 3 from easily accessible unsaturated N-Boc-allylamines
(Scheme 1).
Scheme 1. Synthesis of C5-Functionnalized Oxazolidin-2-
ones 3 from N-Boc-allylamines 1
At first, the intramolecular iodo-cyclization starting from
N‑Boc-N-benzyl-allylamine 1a (R = Bn, R′ = H) was
optimized (see Table S1). The best reaction conditions to
access N‑benzyl-5-iodomethyloxazolidin-2-one 2a were found
to be the use of N-iodosuccinimide (NIS) (1 equiv) in
refluxing THF (c = 0.67 mol·L−1), in a sealed tube for 1 h,
Figure 1. C5-functionalized oxazolidin-2-ones in drugs and natural
products.
Received: March 27, 2020
Despite a large range of synthetic methods leading to such
heterocycles,7 CO2 insertion into amino alcohols, epoxy
amines, or aziridines was developed.8 However, an efficient
strategy allowing the synthesis of oxazolidin-2-ones of type A
by introducing a diversity of R′′/Ar groups at the C5′ position,
at a late stage, would be of interest (Figure 1).
https://dx.doi.org/10.1021/acs.orglett.0c01114
© XXXX American Chemical Society
Org. Lett. XXXX, XXX, XXX−XXX
A

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Letter
leading to 2a which was isolated in 80% yield. Having the best
conditions to access the iodo derivatives 2, the one-pot iodo-
cyclization/cross-coupling was then examined, and the
optimization of the reaction conditions was achieved (Table
1). Based on our previous experience,14 once the iodo-
cyclization to access intermediate 2a was complete, the cross-
coupling of this latter with PhMgBr (1.5 equiv, rate of addition
v = 0.26 mmol·h−1) was explored by screening various cobalt
salts (at 0 °C for 40 min). By using CoCl2 (15 mol %) in the
presence of a diamine ligand such as N,N,N′,N′-tetramethyl-
ethylenediamine (TMEDA, 1 equiv), only traces of the
expected compound 3a were observed, while Co(acac)2 (15
mol %) gave 3a in 9% yield (1H NMR yield) and Co(acac)3
(15 mol %) led to 3a in 11% yield (1H NMR yield) (Table 1,
entries 1−3). Using Co(acac)3 and increasing the excess of
PhMgBr from 1.5 to 3 equiv, 3a was formed in 47% yield (1H
NMR yield) (Table 1, entry 4). Pleasingly, when the addition
rate of PhMgBr was increased from 0.26 to 0.52 mmol·h−1, 3a
was isolated in 74% yield (Table 1, entry 5). In addition, upon
decreasing the catalyst loading of Co(acac)3, from 15 to 10
mol %, and the amount of TMEDA, from 100 to 40 mol %,
with a faster addition rate of PhMgBr (1.04 versus 0.52 mmol·
h−1), 3a could be isolated with a good yield of 76% (Table 1,
entry 6). It is worth mentioning that the use of copper salts
[CuI and CuCl2 (15 mol %)] did not allow the cross-coupling
of the iodo-oxazolidin-2-one intermediate 2a (formed in situ)
with PhMgBr as 3a was not observed (see Table S2).
Furthermore, iron salts [FeCl2, FeCl3 and Fe(acac)3 (15
mol %) in the presence of TMEDA (1 equiv)] allowed the
formation of the oxazolidin-2-one 3a, but in low yield (see
Table S2).
Table 2. Scope of the One-Pot Two-Step Sequence to
Access C5-Functionalized Oxazolidin-2-ones 3a−i from N-
Boc-allylamines 1a and 1b Using Various Arylmagnesium
Bromide
Table 1. Optimization of the Reaction Conditions for the
Cross-Coupling in a One-Pot Sequence to Access
Oxazolidin-2-one 3a from N-Boc-N-benzylallylamine 1a
Using PhMgBr
TMEDA
PhMgBr
v
a
entry [Co] (x mol %) (y mol %) (z equiv) (mmol·h−1
)
3a (%)
a
b
3h and 3i were obtained with 98% purity. Over 3.83 mmol scale
1
2
3
4
5
6
CoCl2 (15)
100
100
100
100
100
40
1.5
1.5
1.5
3
3
3
0.26
0.26
0.26
0.26
0.52
1.04
traces
9
11
47
74
76
(1 g), 3h was isolated with a yield of 33% and 3i with a yield of 22%.
Co(acac)2 (15)
Co(acac)3 (15)
Co(acac)3 (15)
Co(acac)3 (15)
Co(acac)3 (10)
b
the para position of the aryl group such as a methyl or a
methoxy substituent, the corresponding cyclized/coupled
products 3b, 3c, and 3d were isolated in good yields (65%,
68%, and 62% yield, respectively) (Table 2, entries 2−4). The
m-methoxyphenyl Grignard reagent gave also the expected
oxazolidin-2-one 3e in 60% yield (Table 2, entry 5). Sterically
hindered ortho-substituted Grignard reagents such as the
o‑methylphenyl- or the o-methoxyphenylmagnesium bromide
led to the corresponding oxazolidin-2-ones 3f and 3g in 34%
and 37% moderate yields, respectively (Table 2, entries 6 and
7). To access enantioenriched oxazolidin-2-ones, N-Boc,N-
[(R)-phenylethyl]allylamine 1b was treated with PhMgBr, and
under the optimized reaction conditions, the two diastereo-
meric oxazolidin-2-ones 3h and 3i were obtained in a 1:1 ratio
b
a
1H NMR yield determined by using 1,3-dimethoxybenzene as
internal standard. Isolated yield.
b
With the optimized reaction conditions in hand, the scope of
the one-pot, two-step process was examined with various aryl
Grignard reagents and N-Boc-allylamines 1, allowing the access
to C5-functionalized oxazolidin-2-ones (3a−i) (Table 2),
bicyclic oxazolidin-2-ones (3j−l) and a spirocyclic derivative
(3m) (Table 3). When electron-poor substituents are present
in the para position of the aryl Grignard reagent, such as a
fluorine atom or, when electron-rich substituents are present in
B
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bioactive compounds.·5,18,19 Thus, by reacting N-Boc,N-
benzyl-cylohex-2-ene-1-amine 1c, (S)-N-Boc-2-vinylpyrrol-
idine 1d, and N-Boc-2-vinylpiperidine 1e with PhMgBr
under the optimized reaction conditions, the corresponding
bicyclic compounds 3j, 3k, and 3l were isolated in 64% yield
(dr = 96:4), 51% yield (dr = 90:10), and 61% yield (dr =
65:35), respectively (Table 3, entries 1−3). In addition, the
unsaturated N-Boc substrate 1f afforded the spirocyclic
compound 3m, albeit in low yield (11%) but with a good dr
of 95:5 (Table 3, entry 4).
Table 3. Scope of the One-Pot Two-Step Sequence to
Access Bicyclo- and Spiro-oxazolidin-2-ones 3j−m from
N‑Boc-allylamines 1c−f Using PhMgBr
The relative configuration of the stereogenic centers of the
bicyclic oxazolidin-2-one 3j was confirmed by X-ray diffraction
analysis. To explain the formation of 3j, we can envisage that,
after the formation of the iodonium ion intermediate, an anti
attack of the tert-butyl carbamate group on the iodonium
implies than the C−O and C−I bonds are in a trans
relationship, leading to the iodine intermediate 2c. Thereafter,
the cross-coupling of 2c with PhMgBr, catalyzed by
Co(acac)3/TMEDA, was achieved and a new C−C bond
was created, leading the bicyclic compound 3j with the phenyl
group in an equatorial position (Scheme 3).
Scheme 3. Rationalization of the Configuration of the Major
Diastereomer of 3j through the Iodo Cyclization/Cross-
Coupling Sequence
a
Relative stereochemistry not determined.
(determined by 1H NMR analysis of the crude reaction
mixture). These two diastereomers were easily separated by
silica gel column chromatography, and each of them was
isolated in 31% yield (Table 2, entry 8). This sequence of
reactions was scaled up (from 0.22 to 3.83 mmol with an
increase of the addition rate of PhMgBr from 1.04 to 11.47
mmol·h−1), affording 3h and 3i in a 60:40 ratio (determined
1
by H NMR analysis of the crude reaction mixture) and
As a compound has a better chance to be on the market by
“escaping from flatland”,20 the replacement of an aryl group at
the C5′ position of the oxazolidin-2-ones by an aryl
bioisostere, such as cyclopropane, has been envisaged. Thus,
N-Boc-N-benzylallylamine 1a was treated, under the previously
optimized reaction conditions, with cyclopropylmagnesium
bromide. However, the use of Co(acac)3, as well as other
cobalt or iron salts was not effective as 3n was not formed (see
Table S3). Due to this failure, the use of copper salts was
explored to realize the coupling between the iodo-oxazolidin-2-
one 2a, intermediately formed, and cyclopropylmagnesium
bromide (1.2 equiv, rate of addition v = 1.04 mmol.h−1, 0 °C, 1
h) (Table 4). Different copper salts were screened such as
Li2CuCl4 (10 mol %) and CuCl2 (10 mol %); however, these
catalysts did not produce the desired oxazolidin-2-one 3n
(Table 4, entries 1 and 2). On the contrary, when CuI (10 mol
%) was utilized, the oxazolidin-2-one 3n was formed in 31%
yield (1H NMR yield) (Table 4, entry 3). Increasing the excess
of cyclopropylmagnesium bromide from 1.2 to 3 equiv led to
3n in 53% yield (1H NMR yield) (Table 4, entry 4). Adding
TMEDA (40 mol %) to the reaction mixture allowed the full
conversion of 2a to 3n which was obtained in 64% yield (1H
NMR yield) (Table 4, entry 5). Decreasing the catalytic
loading of CuI from 10 to 5 mol % in the presence of TMEDA
isolated in 33% and 22% yields, respectively, after purification
by silica gel column chromatography.15
As the oxazolidin-2-ones offer the opportunity to access
amino alcohols, 3i was treated with NaOH (in refluxing EtOH,
16 h) to afford 4 in 76% yield (Scheme 2). Compound 4 was
transformed to its crystalline ammonium chloride salt, and the
absolute configuration of the carbon substituted by the
hydroxyl was determined by X-ray diffraction analysis. This
analysis confirmed at the same time the absolute configuration
of the C5 stereogenic center of the oxazolidin-2-one 3i. It is
worth noting that the amino alcohol 4 can be utilized to
synthesize various heterocycles.16
Bicyclo- and spiro-heterocycles containing an oxazolidin-2-
one core appear to be interesting compounds as they can be
precursors of azasugars17 as well as natural products6,18 and/or
Scheme 2. Oxazolidin-2-one Ring-Opening: From N-
Benzyl-5-benzyloxazolidin-2-one 3i to Amino Alcohol 4
C
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Letter
(40 mol %) afforded 3n, which was isolated in 66% yield
(Table 4, entry 6). It is worth mentioning that the catalytic
loading of CuI can be decreased from 5 to 2.5 mol % in the
presence of TMEDA (40 mol %) as 3n was obtained in a
AUTHOR INFORMATION
■
Corresponding Author
Janine Cossy − Molecular, Macromolecular Chemistry and
Materials, ESPCI Paris, PSL University, CNRS, 75005 Paris,
France; orcid.org/0000-0001-8746-9239;
Email: janine.cossy@espci.fr
1
similar yield (64%, H NMR yield) (Table 4, entry 7).
Table 4. Optimization of the Reaction Conditions for the
Cross-Coupling in a One-Pot Sequence to Access
Oxazolidin-2-one 3n from N-Boc-N-Benzylallylamine 1a
Using Cyclopropylmagnesium Bromide
Author
Pauline Chaumont-Olive − Molecular, Macromolecular
Chemistry and Materials, ESPCI Paris, PSL University, CNRS,
75005 Paris, France; orcid.org/0000-0002-4137-3079
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.0c01114
Notes
The authors declare no competing financial interest.
TMEDA
cyclopropylmagnesium
bromide (z equiv)
a
entry [Cu] (x mol %) (y mol %)
3n (%)
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1.2
3
3
3
none
traces
31
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ASSOCIATED CONTENT
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* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.0c01114.
Experimental procedures and spectral data for all
compounds (PDF)
Accession Codes
CCDC 1991426−1991427 contain the supplementary crys-
tallographic 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.
D
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Letter
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https://dx.doi.org/10.1021/acs.orglett.0c01114
Org. Lett. XXXX, XXX, XXX−XXX