Expedient stereospecific Co-catalyzed tandem C-N and C-O bond formation of: N -methylanilines with styrene oxides

Article abstract of DOI:10.1039/c8cc06223d

Cobalt(ii)-catalyzed stereospecific coupling of N-methylanilines with styrene oxides is developed via tandem C-N and C-O bond formation using tert-butyl hydroperoxide (TBHP) as an oxidant. Optically active epoxide can be reacted with high optical purity.

Full text of DOI:10.1039/c8cc06223d

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc
first methanofullerene derivatives of Sc
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N@C2n (2n
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DOI: 10.1039/C8CC06223D
Authors
†
†
†
Vanaparthi Satheesh, Sundaravel Vivek Kumar, and Tharmalingam Punniyamurthy*
Affiliations
†
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati 781039, India. E-mail:
tpunni@iitg.ac.in
Acknowledgements
We thank Science and Engineering Research Board (SERB) (EMR/2015/43) and Council of Scientific
and Industrial Research (02(0088)/12/EMR-II) for the financial support. V.S thanks CSIR for Senior
Research Fellowship and S.V.K. thanks SERB for National Postdoctoral Fellowship
(PDF/2016/001460). We also thank Central Instrumental Facility, Indian Institute of Technology
Guwahati for the NMR facilities.

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DOI: 10.1039/C8CC06223D
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Expedient stereospecific Co-catalyzed tandem C-N and C-O bond
formation of N-methylanilines with styrene oxides
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Cobalt(II)-catalyzed stereospecific coupling of N-methylanilines acetonitrile and THF furnished 32-48% yields (entries 8-11).
with styrene oxides is developed via a tandem C-N and C-O bond Screening of the oxidants such as DTBP, 30% H and O led to
formation using tert-butyl hydroperoxide (TBHP) as an oxidant. inferior results (entries 12-14). Control experiments confirmed
2
O
2
2
Optically active epoxide can be reacted with high optical purities.
2 2
that the combination of Co(OAc) ·4H O and TBHP is essential for
this transformation (entries 15-16).
1
1
,3-Oxazolidines are unique class of heterocycles and found in
2
numerous biologically important structural scaffolds including
quinocarcin, cyanocycline A and tetrazomine, which display
antibacterial, antitubercular, antiproliferative and anticancer
3
properties (Figure 1). In addition, they are often utilized as the
synthetic intermediates, auxiliaries, ligands and catalysts for
4
organic transformation. Considerable efforts are thus made on
the development of effective synthetic methods for their
Figure 1. Some selected examples of biologically active 1,3-oxazolidine scaffolds.
5
,6
construction. Recently, Terada and co-workers reported a
chiral organosuperbase-catalyzed coupling of epoxides with
7
imines to produce chiral 1,3-oxazolidines (Scheme 1a). Cobalt
is less expensive, readily available, environmentally benign and
active centre of a group of coenzymes. Much attention are thus
devoted on the development of Co-based catalytic systems.8,9
In addition, a catalytic C-H functionalization provides a powerful
synthetic tool for the transformation of the simple substrates
10,11
into complex molecules with structural diversity.
Herein, we
present a stereospecific cobalt(II)-catalysed tandem C-N and C-
O bonds formation of N-methylanilines with styrene oxides to
furnish 1,3-oxazolidines in the presence of TBHP via a one-pot
sequence of S 2 ring opening of epoxide, C-H functionalization
N
and cyclization. Optically active epoxide can be coupled with
high enantiomeric purities.
First, we optimized the reaction employing N-methylaniline
1a with styrene oxide 2a as the model substrates using a series
of Cu(II), Fe(II) and Co(II) salts at varied temperatures (Table 1).
Gratifyingly, the coupling occurred to give 1,3-oxazolidine 3a in
Scheme 1. Recent methods for the synthesis of 1,3-oxazolidines from epoxides.
5
8% yield when the substrates were stirred with 10 mol% of
Cu(OTf) at 60 ˚C for 1 h in CH Cl , followed by treatment with
2
2
2
Having optimized the reaction condition, the scope of the
procedure was inspected for a series of N-methylanilines 1b-q
with 2a as a standard substrate (Table 2). N-Methylaniline
bearing 2-methyl 1b group underwent reaction to give the ring
TBHP and stirring for 2 h (entry 1). Subsequent screening of the
catalysts revealed that Co(II) salts are superior to that of Cu(II)
and Fe(II) salts (entries 2-7). The best results observed utilizing
Co(OAc) ·4H O with 67% yield (entry 6). (CH Cl) was found to
2 2 2 2
the solvent of choice, giving 73% yield, whereas toluene,
opening amino alcohol
1
A in 81% yield and no cyclization was
observed that may be to the steric hindrance of the methyl
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J. Name., 2013, 00, 1-3 | 1
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Journal Name
Table 1 Optimization of the reaction conditionsa,b
with N-methylanilines having 4-chloro 1g, 4-methyl 1k and 3-
ethyl 1c groups can be readily accomplished to furnish the
View Article Online
DOI: 10.1039/C8CC06223D
oxazolidines 3ac-ae in 71-76% yields.
Entry Catalyst
Oxidant
TBHP
Solvent
3a (%)b
c
d
e
1
Cu(OTf)
Cu(OAc)
Fe(acac)
Fe(OAc)
Co(acac)
Co(OAc)
CoCl
2
CH
2
2
2
2
Cl
2
2
2
2
34, 42, 48, 58
2
3
4
5
6
7
8
9
2
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
DTBP
CH
CH
CH
CH
CH
CH
Cl
Cl
Cl
Cl
Cl
Cl
45
26
33
54
67
60
73
48
45
32
48
20
14
n.d.
n.d.
2
2
2
2
2
2
2
2
•4H
2
O
2
2
2
Co(OAc)
Co(OAc)
Co(OAc)
Co(OAc)
Co(OAc)
Co(OAc)
Co(OAc)
Co(OAc)
-
2
•4H
2
•4H
2
•4H
2
•4H
2
•4H
2
•4H
2
•4H
2
•4H
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
(CH
Toluene
CH CN
THF
2
Cl)
2
1
0
1
2
3
4
5
6
3
1
1
1
1
1
1
(CH
(CH
(CH
(CH
(CH
2
Cl)
2
Cl)
2
Cl)
2
Cl)
2
Cl)
2
30% H
2
O
2
2
2
2
2
O
2
-
TBHP
a
Reaction conditions. 1a (0.50 mmol), 2a (0.50 mmol), catalyst (10 mol %), solvent
b
(2 mL), 60° C, 2 h, then oxidant (1 mmol), 60 °C, 1 h. Isolated average yield of two
Scheme 2 Reaction of different N-methylanilines
Reaction conditions: 1b-q (0.50 mmol), 2a (0.50 mmol), Co(OAc)
CH Cl
1
with styrene oxide 2a
.
,
c
d
e
.
runs. Room temperature. 50° C. 1.5 eq. TBHP was used. n.d. = not detected
2
·4H O
2
(
2
2
)
2
(2 mL), 60 °C, 2 h, then TBHP (1 mmol), 60 °C, 1-3 h. Isolated yield.
functionality. However, the reaction of the substrates bearing
3
-ethyl 1c, 3-methyl 1d and 3-trifluoromethyl 1e substituents
The reaction condition was further extended to the coupling
of tetrahydroisoquinoline with styrene oxides (Scheme 4).
Pleasingly, the reactions readily occurred to produce the tricylic
afforded the target heterocycles 3c-e in 65-72% yields. Similar
results observed with the substrates containing 4-bromo 1f, 4-
chloro 1g, 4-fluoro 1i, 4-ethyl 1j, 4-methyl 1k and 4-isopropyl 1l
substituents, giving 3f-g and 3i-l in 72-77% yields, whereas 1h
having 4-cyano group produced the ring opening amino alcohol
A as a sole product in 68% yield, which may be due to the
2
delocalization of nitrogen lone pair with aryl ring. Similarly, the
reactions of N-methylpyridin-4-amine 1m and N-benzylaniline
1n, furnished the amino alcohols A and A in a trace amount
3 4
and 88% yield, respectively, which could be presumably due to
the steric hindrance to form the imine cation or the complex
formation of Co species with pyridine nitrogen. However, the
reaction of the substrates containing 3,4-dimethyl 1o, 3,5-
dichloro 1p and 3,5-dimethyl 1q substituents can be performed
to afford 3o-q in 67-78% yields.
4
heterocyclic scaffolds 5a-c with good diasteroselectivity in 68-
7
5 % yields.
To reveal the stereoselectivity, we studied the reaction of (R)-
styrene oxide 2a’ with a series of N-methylanilines (Scheme 5).
To our delight, the reaction took place stereospecifically to give
the 1,3-oxazolidines in high optical purities. For example, N-
methylaniline having 3-ethyl group 1c underwent reaction to
give 3c’ in 98% ee and 75 % yield. Similar results observed with
N-methylanilines containing 4-bromo 1f, 4-chloro 1g, 4-fluoro
1
i
, 4-ethyl 1j, 4-methyl 1k and 4-isopropyl 1l groups, providing
3
f’, 3g’ and 3i’-l’ in 95-98% ee and 70-76% yields. In addition, N-
methylanilines having methyl groups at 3,4- 1o and 3,5- 1q
positions could be coupled to give 3o’ and 3q’ in 97% ee and 73-
Next, we studied the scope of the procedure for the reaction
of styrene oxides 2b-l with N-methylaniline 1a as the standard
substrate (Scheme 3). The reaction of styrene oxides having 2-
chloro 2b, 3-methoxy 2c, 3-methyl 2d, 3-fluoro 2e and 3-nitro
7
6% yields. These results suggest that N-methylaniline reacts
2
12
with epoxide presumably via a S
N
pathway.
To gain insight in the catalytic cycle, we studied the coupling
of 1a and 2a as the representative example using BHT radical
inhibitor (Scheme 6). ESI-Mass analysis of the reaction mixture
2
f
substituents occurred to afford the desired 3r-v in 58-74%
yields. Similarly, the epoxides bearing 4-acetoxy 2g, 4-bromo
, 4-chloro 2i and 4-fluoro 2j groups are well tolerated to
revealed the formation BHT-adduct
see SI). The formation of suggests that a radical intermediate
may be involved. Our effort to isolate was, however, failed
due to the formation of a trace amount. When we reacted
using Co(OAc) •4H O and TBHP, the oxidative cyclization
6 and the amino alcohol A
7
2
h
(
6
furnish the oxazolidines 3w-z in 75-80% yields, whereas the
reaction of 2k containing 4-cyano group yielded the uncyclized
6
A
7
amino alcohol
underwent the nucleophilic ring opening at the less hindered
methylene carbon to give in 90% yield, which showed no
cyclization. However, the reaction of the epoxides 2g and 2i
5
A in 82% yield. Furthermore, 2-ethylene oxide 2l
2
2
occurred to give 3a in 80% yield, which suggests that N-
A
6
2
| J. Name., 2012, 00, 1-3
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Journal Name
COMMUNICATION
methylaniline reacts with epoxide to give an amino alcohol that the major diastereomer
leads to a cyclization via C(sp )-H functionalization (Scheme 7). like transition states (TS)
5
can be exemplified through a chair
View Article Online
DOI: 10.1039/C8CC06223D
3
e and f (Scheme 9). TS e is favoured
because of the evading the undesired interaction, whereas TS
has 1,3-diaxial interaction.
f
Scheme 5 Reaction of different N-methylanilines
1
with (R)-styrene oxide
2
·4H O,
2
a'. Reaction conditions: (0.50 mmol), 2a’ (0.50 mmol), Co(OAc)
1
2
solvent (2 mL), 60° C, 2 h, then TBHP (2 equvi), 60 °C, 1-3 h. Isolated yield.
Scheme 3 Substrate scope of N-methylanilines
Reaction conditions: N-methylaniline (0.50 mmol), 2b-l (0.50 mmol),
Co(OAc) ·4H , solvent (2 mL), 60° C, 2h, then TBHP (1 mmol), 60 °C, 1-3 h.
Isolated yield.
1 and styrene oxides 2b-l.
2
2
O
Scheme 6 Radical trapping experiment.
Scheme 4 Reaction of tetrahydroisoquinoline
and 2j. Reaction conditions: (0.50 mmol),
4
with styrene oxides 2a
, 2c
4
2
(0.50 mmol), Co(OAc) ·4H
2
2
O
,
Scheme 7 Control experiment.
solvent (2 mL), 60° C, 2 h, then TBHP (1 mmol), 60 °C, 1 h. Isolated yield. dr
1
calculated from 600 MHz H NMR.
Based on these experimental results and the literature,8,9
proposed catalytic cycle is shown in Scheme 8. The chelation of
Co(II) with epoxide oxygen , may facilitate the nucleophilic ring
opening with N-methylanilines to give via S 2 pathway. The
latter can convert into the radical cation via a single electron
transfer (SET) to Co(III) species, which can be produced from
Co(II) with TBHP. Homolytic cleavage of the C-H bond in using
t-butoxy radical/ t-butylperoxy radical can give imine ion that
can lead to intramolecular cyclization to furnish the heterocycle
a
a
b
N
c
c
d
13
3
. The Co(II)-Co(III) triggered cleavage of TBHP can be give the
t-Butoxy radical. The proposed catalytic cycle also explains the
Scheme 8 Proposed reaction pathway.
requirement of an excess TBHP. Furthermore, the formation of
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8
Scheme 9 Stereochemical model.
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In conclusion, we presented a Co(II)-catalyzed stereospecific
coupling of N-methylanilines with styrene oxides to furnish 1,3-
oxazolidines via a tandem C-N and C-O bonds formation in the
presence of TBHP. Optically active epoxide can be coupled with
high enantiomeric purities.
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| J. Name., 2012, 00, 1-3
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Please d Co hn eomt Ca do jmu smt margins
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DOI: 10.1039/C8CC06223D
Journal Name
COMMUNICATION
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
H
N
O
NH
examples
O
Ar'
Me
Ar
*
*
Ar
N
O
N
3
31 examples
Co
Ar
Stereospecific
10 examples
up to 99% ee
'Ar
Substrate scope
Functional group tolerance
A Co(II)-catalyzed stereospecific sequential C-N and C-O bond formation of styrene oxides with N-methylanilines has been developed.
Optically active epoxide can be coupled with high enantiomeric purities.
This journal is © The Royal Society of Chemistry 20xx
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