Rhodium(iii)-catalyzed diamidation of olefins: Via amidorhodation and further amidation

Article abstract of DOI:10.1039/d0cc00952k

Rh(iii)-catalyzed synthesis of vicinal diamides has been realized via elaboration of an authenticated Rh-C(sp3) species generated via initial intramolecular amidorhodation of olefins. The second amidation was achieved using both electrophilic and nucleophilic amidating reagents. The reactions proceeded under mild conditions with good yield, broad substrate scope, and excellent functional-group tolerance.

Full text of DOI:10.1039/d0cc00952k

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Rhodium(III)-Catalyzed Diamidation of Olefins via
Amidorhodation and Further Amidation
Jinlei Wang, Guangfan Zheng, Xingwei Li*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
1
1
3
Abstract: Rh(III)-catalyzed synthesis of vicinal diamides has been particularly by Rh(III) catalysis (Scheme 1b). C(sp )-H activation
3
3
realized via elaboration of an authenticated Rh-C(sp ) species generates a Rh-C(sp ) intermediate that can be functionalized
1
1b
generated via initial intramolecular amidorhodation of olefins. The by a diverse array of coupling reagents such as alkyne,
1
2
13
3k-l, 14
second amidation was achieved using both electrophilic and olefins, diazo compounds, and aminating reagents.
We
nucleophilic amidating reagents. The reactions proceeded under reasoned that such organorhodium could be alternatively
mild conditions with good yield, broad substrate scope, and accessed via cyclization of an olefin bearing a proximal nitrogen
excellent functional-group tolerance
nucleophile. Of note, although cyclization of alkynes bearing a
proximal nucleophile has been studied in Rh(III)-catalyzed
coupling reactions, the cyclization of olefins has been rarely
studied. We now report diamidation of olefins using both
electrophilic and nucleophilic amidating reagent, where a
rhodium(III) alkyl species has been authenticated as an
intermediate (Scheme 1c).
Nitrogen-containing organics, especial vicinal diamines,
represent an important family that have been employed as
synthetic building blocks, biologically active molecules, and
15
1
privileged ligands in transition metal catalysis. Consequently,
great efforts have been made in nitrogenation of diverse
substrates.2 Among reported methods, metal-catalyzed C-N
coupling reactions have been increasingly employed for direct
a) Metal-Catalyzed Diamination of Alkenes
3
functionalization of readily available substrates. Traditional C-
X
NH
X
CH2
R
Pd, Cu, Ni, Ir
N
R
amide, NFSI
amine, or azide
+
N coupling strategies include the Buchwald-Hartwig coupling,
the Goldberg reaction, and the Chan-Lam reaction. However,
they may suffer from limited efficiency or compatibility during
introduction of two nitrogen groups. Significantly, Shi and
others made important progress in diamination of olefins using
NR'2
b) sp3 C-H Functionalization via M-C(sp ) Formation
3
Rh(III)
DG CH3
DG CH2 FG
DG = directing group
FG = functional group
Coupling Reagent
4
strained aminating reagents. Subsequently, diamination of
5
6
7
8
diverse olefins have been realized using Pd, Cu, Ni, and Ir
catalysts (Scheme 1a), as in the reports by Muinz, Wang, Rovis,
and others.9 Despite the significant progress, the coupling
3
c) Olefin Diamidation via Rh-C(sp ) Formation(This Work)
O
O
O
N
O
Rh(III)
systems suffer from intramolecular diamination or employment
N
N
+
O
N
Py
Ph
H
with or w/o
oxidant
6
a
or
ArSO2NH2
of limited classes of nitrogen sources such as amides,
NHR
amines,6 NFSI,
h-i
3f-g,10
and organoazides. Therefore, it is
6b
necessary to develop new diamination/diamidation methods
using readily available electrophilic and nucleophilic reagents.
The successful development of olefin diamination boils down
3
Scheme 1. Formation of C(sp )-M Bond en route to C-N Coupling.
to generation and subsequent efficient transformation of a M-
We initially investigated olefin diamidation using reactive
C(sp ) bond. Regarding this organometallic species, lessons can dioxazolone as the external, electrophilic amidating reagent.
be drawn from chelation-assisted C(sp )-H activation, N-substituted 2-(prop-1-en-2-yl)benzamide (1a) was employed
3
16
3
as a substrate. It was found that the N-group had profound
effects on the reaction efficiency under Rh(III)-catalyzed
reaction conditions (Table S1 in the Supporting Information).
Key Laboratory of Applied Surface and Colloid Chemistry of MOE, School of Chemistry
and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China
Thus, employment of N-OMe or -NHPh group only resulted in
E-mail: lixw@snnu.edu.cn
†Electronic Supplementary Information (ESI) available: Experimental procedures
and characterization data of all compounds. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Journal Name
simple cyclization of the olefin (3aa', 24-84% yield), indicating conditions in superior yields. The negative effect of p-NO
2
and
View Article Online
DOI: 10.1039/D0CC00952K
that the cyclization proceeded well but the Rh-C bond was m-CF
3
groups was resolved by rhodium catalysis (3af and 3ap).
rapidly protonolyzed. To ensure stability of the organorhodium Introduction of m-Me and -Cl groups was also tolerated (3ak,
intermediate, an N-Py chelating group was installed. Indeed, the 3al), and the m-F group greatly favored the reaction, affording
desired diamidation product 3aa started to be observed in DCE the desired product (3aj) in excellent yield (97%). An o-methyl-
(entries 6-8), and the simple cyclization by-product was substituted dioxazolone also reacted smoothly, yielding
inhibited when the acid additive was omitted (entry 8). product 3am with moderate efficiency. In addition, furyl-,
We next conducted further optimization studies using thienyl-, and alkyl-substituted dioxazolones were also
substrate 1a (Table S2 in the Supporting Information). It was compatible (3an, 3ao, 3aq, and 3as).
2 2
found that both the [Cp*RhCl ] catalyst and silver salt were
essential to the catalytic system (entries 3-4). After screening
several other parameters (entries 5-18), we found that air
atmosphere was beneficial for the reaction and AgSbF turned
6
out to be the optimal activator, and the desired product 3aa
O
O
R2
Condition A or B
AgSbF6 (16 mol %)
Air, 16 h
N
O
N
H
N
N
R2
+
N
O
R1
Ph
O
HN
Ph
R1
1
2a
4
O
Conditions A: [Cp*RhCl2]2 (4 mol %), DCE, 50°C,
Conditions B: [Cp*Co(CO)I2] (8 mol %), Zn(OAc)2 (2.0 equiv), TFE, 100°C,
was isolated in 83% yield (entry 7). Given reported comparable
1
6e
catalytic activities in amidation, the Co(III) congener was also
O
O
O
O
explored, and 3aa was eventually isolated in 76% yield when
N
Py
N
Py
N
Py
N
[
Cp*Co(CO)I
2
] (8 mol %) was used as a catalyst in the presence
in TFE solvent (see Table S3 in the Supporting
N
4-PhC6H4
4-ClC H
Ph
4-PhC6H4
6
4
of Zn(OAc)
2
HN
Ph
HN
Ph
HN
Ph
HN
Ph
Information).
O
O
O
O
4
ba, 64% (Rh); 24% (Co) 4ca, 81% (Rh); 35% (Co) 4da, 84% (Rh); 22% (Co) 4ea, 94% (Rh); 41% (Co)
O
O
N
O
Condition A or B
AgSbF6 (16 mol %)
O
C
l
O
CH3
O
O
C
F
3
N
N
+
H
O
N
Py
R
O
Air, 16 h
NH
R
N
N
N
N
1a
2
3
O
N
N
N
N
Conditions A: [Cp*RhCl2]2 (4 mol %), DCE, 50°C,
Conditions B: [Cp*Co(CO)I2] (8 mol %), Zn(OAc)2 (2.0 equiv), TFE, 100°C,
HN
Ph
HN
Ph
HN
Ph
HN
Ph
O
O
O
O
O
O
O
O
N
Py
N
Py
N
Py
N
Py
4fa, 84% (Rh); 42% (Co) 4ga, 44% (Rh); 24% (Co) 4ha, 86% (Rh); 36% (Co) 4ia, 64% (Rh); < 5% (Co)
Cl
CH3
CF3
NH
NH
NH
NH
O
O
O
O
O
O
Unsuccessful substrates
O
3
aa, 83% (Rh); 76% (Co)
3ab, 90% (Rh); 47% (Co)
3ac, 71% (Rh); 65% (Co)
3ad, 71% (Rh); 28% (Co)
N
Py
N
Py
O
O
O
O
O
Et
Cy
N
Py
N
Py
N
Py
N
Py
N
N
N
N
OMe
NO2
CO2Me
t-Bu
HN
Ph
HN
Ph
H
NH
NH
NH
NH
H
O
O
CH3
O
O
O
O
H
3ae, 84% (Rh); 38% (Co)
3af, 32% (Rh); < 5% (Co)
3ag, 72% (Rh); 34% (Co)
3ah, 65% (Rh); 64% (Co)
4ja, 84% (Rh); 37% (Co) 4ka, 67% (Rh); <5% (Co)
O
O
O
O
N
Py
N
Py
N
Py
N
Py
F
NH
NH
NH
NH
Scheme 3. Scope of Alkenes in Amidation Reactions. Reaction conditions: 1 (0.1
mmol), 2a (0.2 mmol), solvent (1.5 mL) under air for 16 h. Isolated yield.
O
O
F
O
CH3
O
Cl
3
ai, 83% (Rh); 74% (Co)
3aj, 97% (Rh); 52% (Co)
3ak, 82% (Rh); 57% (Co)
3al, 74% (Rh); 36% (Co)
O
O
O
O
N
Py
N
Py
N
Py
N
Py
O
S
The scope of alkene substrates was next explored using 2a as
a coupling partner (Scheme 3). As expected, the Co(III)-
catalyzed system generally gave lower reactivity. As for the
NH
NH
NH
NH
O
O
O
O
CF3
MeO
3
am, 45% (Rh); 28% (Co)
3an, 87% (Rh); 30% (Co)
3ao, 93% (Rh); 25% (Co)
3ap, 59% (Rh); < 5% (Co)
O
O
O
Cl
1
N
Py
N
Py
N
Py
rhodium-catalyzed system, variation of R from methyl group
NH
NH Bn
NH C7H15-n
(1a) to ethyl, cyclohexyl, and substituted aryl groups had little
O
Cl
O
O
3
aq, 66% (Rh); 42% (Co)
3ar, 47% (Rh); 39% (Co)
3as, 88% (Rh); 71% (Co)
influence on the activity of the diamidation(4ba-4ea, 4ja-4ka).
2
By varying the R group in the pyridine ring to alkyl, halogen,
Scheme 2. Scope of Dioxazolones in Amidation Reaction. Reaction conditions: 1a
0.2 mmol), 2 (0.2 mmol), solvent (1.5 mL) under air for 16 h. Isolated yield.
3
and CF groups, and the reactions also proceeded smoothly to
(
yield the corresponding products (4fa-4ia) in satisfactory yields.
Unexpectedly, both vinyl and internal olefin were incompatible
with the standard reaction condition.
With the optimal catalytic conditions in hand, the scope of
the two metal-catalyzed systems were next examined (Scheme
). The Co(III)-catalyzed method generally afforded the target
product in low to moderate yield, and p-NO and m-CF group-
substituted dioxazolones failed to undergo any coupling with
a. The low yield of this system is probably due to catalyst
decomposition, and this negative influence has been observed
in our reported work. To our delight, this limitation was
resolved when our Rh(III)-catalyzed conditions were applied
conditions A). Further studies revealed that dioxazolones
bearing an electron-donating (3ac, 3ae, and 3ah), -withdrawing
3ad and 3ag), or halogen group (3ab and 3ai) at the para
position coupled smoothly under the rhodium-catalyzed
To better explore the scope of the amidating reagents, we
next investigated aryl sulfonamides as nucleophilic amidating
2
2
3
3
l,m
reagents in the presence of PhI(OAc)
that aryl sulfonamides bearing an electron-withdrawing group
p-CF and p-CN) in the phenyl ring underwent diamidation in
2
oxidant. It was found
1
(
3
1
6e
good yields (4aa, 4ad) when catalyzed by a cationic Rh(III)
catalysts in the presence of NaOAc (Scheme 4). Meanwhile, p-
Cl and p-Me substituted aryl sulfonamides exhibited higher
reactivity under the same conditions (4ab and 4ac).
Comparably high efficiency was observed for a phenyl-
substituted alkene (4ae and 4af).
(
(
2
| J. Name., 2012, 00, 1-3
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intermediate D. Elimination of the CO
2
produces a rhodium(V)-
View Article Online
DOI: 10.1039/D0CC00952K
O
O
[
Cp*Rh(MeCN)3][SbF6]2 (8 mol %)
PhI(OAc)2 (1.5 equiv)
nitrene species E, which undergoes nitrene insertion to give a
seven-membered amidate species F. Protonolysis of the Rh-N
bond releases the diamidated product 3aa together with
regeneration of the active Rh(III) catalyst.
N
H
N
+
Ar-SO NH
2
2
N Py
NaOAc (50 mol %)
rt, 16 h
NHSO Ar
R
2
R
1
4
O
N
O
O
Py O
NH S
N
Py O
NH S
N
Py O
NH S
O
O
O
O
O
3aa
Cp*RhX2
X = SbF6
1a
HX
HX
CF3
CH3
Cl
Cl
O
A
O
4aa, 88%
4ab, 95%
4ac, 98%
O
O
O
N
B
N
N
N
X
Cp
Rh
N
Py O
N
Py O
N
Py O
NH S
Rh
Cp
X
O
N
NH
S
NH
S
F
Ph
Ph
O
CN
CN
Ph
4ad, 71%
4ae, 88%
4af, 88%
O
O
N
Scheme 4. Scope of Sulfonamides in Amidation. Reaction conditions: 1 (0.1 mmol),
Sulfonamides (0.1 mmol), DCM (1.5 mL) under air for 16 h. Isolated yield.
HX
N
3aa,
N
N
X
Rh
Rh
Cp
C
E
N
Cp
X
O
To gain insight into the mechanism of the diamidation
system, several experiments have been performed (Scheme 5).
Subjection of the simple cyclization product 3aa' to the
standard condition only led to recovery of this reactant (Scheme
Ph
O
CO2
N
2a
N
X
Rh
O
O
Cp
N
O
5
a), and the same scenario was observed in amidation using
D
Ph
TsNH . This suggests that the reaction should not proceed via
2
cyclization with subsequent pyridine-directed C-H activation. To
explore the putative Rh(III)-alkyl intermediate, a stoichiometric
amidorhodation reaction has been conducted, from which
rhodacycle 5 was isolated as a single diastereomer (90% yield)
and was characterized by X-ray crystallography (CCDC1957959).
Complex 5 proved to be catalytically active for the coupling of
Scheme 6. Proposed Mechanism.
In summary, we have realized Rh(III)/Co(III)-catalyzed
diamidation of amide-tethered olefins using dioxazolones and
arylsulfonamides as different classes of amidating reagents. The
reaction proceeded via initial intramolecular amidorhodation of
1
a and 2a (Scheme 5c). Thus, it is a plausible intermediate or a
the olefin to generate
a Rh(III)-methyl species that is
direct precursor to this intermediate.
functionalized by both electrophilic and nucleophilic amidating
reagents. The coupling systems were conducted under mild
conditions with high efficiency. In addition, the Rh(III)- and
Co(III)-catalyzed have been compared. This strategy offers a
rapid entry to vicinal diamides and might be useful in synthesis
a) Control Experiment
O
[
Cp*RhCl2]2 (4 mol %)
AgSbF6 (16 mol %)
2
a
1a
N Py
3aa
DCE, 50 oC, 16 h
standard
84%
conditions
1
d, 18
of biologically active molecules.
3aa'
b) Synthesis of a Rh(III)-Alkyl Complex
Cp*
[
Cp*RhCl2]2 (0.5 equiv)
NaOAc (6 equiv)
Rh Cl
Acknowledgements
N
1a
N
O
DCM, r.t.
We acknowledge the financial support for this work from the
NNSFC (21525208) and the Shaanxi Normal University.
5
(90%)
c) Catalytic Activity of the Rh(III)-Alkyl Complex
O
O
Conflicts of interest
5
(8 mol %)
O
O
N Py
NH
N
N
N
AgSbF6 (16 mol %)
+
O
H
DCE, 50 °C, Air, 16 h
Ph
There are no conflicts of interest to declare.
Ph
O
1a
2a
3aa, 64% yield
Notes and references
Scheme 5. Mechanistic Studies.
1
For reviews on 1, 2-diamines, see: (a) K. Muniz, Acc. Chem.
Res., 2018, 51, 1507. (b) X. Zhang and S.-L. You, Chem., 2017,
Based on the above observations and reported diamination
3
, 919. (c) D. Lucet, T. Le Gall and C. Mioskowski, Angew.
of alkenes,8
pathway (Scheme 6). The catalytic cycle starts from an active
catalyst [RhCp*X ] (X = SbF ) species A. Subsequent chelation of
, 16e-f, 17
we proposed a plausible mechanistic
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6
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Olefin complex B is proposed to undergo migratory insertion of
the Rh−N bond to give a Rh(III)-alkyl C that is stabilized by
pyridyl chelation. Coordination of dioxazolone 2a gave an
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R.-J. Song and J.-H. Li, Chem. Commun. 2015, 51, 13550. (c) D.
Y. Li, H. J. Chen and P. N. Liu, Angew. Chem., Int. Ed. 2016, 55,
373. (d) Y. Li, R. Pi, X.-H. Ouyang, R.-J. Song and J.-H. Li, Org.
Lett. 2019, 21, 397.
4
5
(a) H. Du, B. Zhao and Y. Shi, J. Am. Chem. Soc. 2007, 129, 762.
(
b) H. Du, W. Yuan, B. Zhao and Y. Shi, J. Am. Chem. Soc. 2007,
1
7
1
1
29, 11688. (c) L. Xu, H. Du and Y. Shi, J. Org. Chem. 2007, 72,
038. (e) R. G. Cornwall, B. Zhao and Y. Shi, Org. Lett. 2013,
5, 796. (f) H. Du, B. Zhao, W. Yuan and Y. Shi, Org. Lett. 2008,
0, 4231. (g) H. Zheng, Y. Zhu and Y. Shi, Angew. Chem., Int. 16 (a) Y. Park, K. T. Park, J. G. Kim and S. Chang, J. Am. Chem. Soc.
Ed. 2014, 53, 11280. (h) J. Song, Z.-J. Zhang, S.-S. Chen, T. Fan
and L.-Z. Gong, J. Am. Chem. Soc. 2018, 140, 3177.
Selected examples on Pd-catalyzed diamination: (a) K. Muniz,
J. Am. Chem. Soc. 2007, 129, 14542. (b) J. Streuff, C. H.
Hövelmann, M. Nieger and K. Muñiz, J. Am. Chem. Soc. 2005,
2015, 137, 4534. (b) J. Park and S. Chang, Angew. Chem., Int.
Ed. 2015, 54, 14103. (c) Y. Park, J. Heo, M.-H. Baik and S.
Chang, J. Am. Chem. Soc. 2016, 138, 14020. (d) N. K. Mishra,
Y. Oh, M. Jeon, S. Han, S. Sharma, S. H. Han, S. H. Um and I. S.
Kim, Eur. J. Org. Chem. 2016, 2016, 4976. (e) F. Wang, L. Jin, L.
Kong and X. Li, Org. Lett. 2017, 19, 1812. (f) F. Wang, H. Wang,
Q. Wang, S. Yu and X. Li, Org. Lett. 2016, 18, 1306. (g) P. W.
Tan, A. M. Mak, M. B. Sullivan, D. J. Dixon, and J. Seayad,
Angew. Chem. Int. Ed. 2017, 56, 16550. (h) B. Khan, V.
Dwivedi, and B. Sundararaju, Adv. Synth. Catal. 2020, 362,
1195.
1
27, 14586. (c) K. Muñiz, L. Barreiro, R. M. Romero and C.
Martínez, J. Am. Chem. Soc. 2017, 139, 4354. (d) B. Zhao, H.
Du, S. Cui and Y. Shi, J. Am. Chem. Soc. 2010, 132, 3523. (e)
M.-S. Wu, T. Fan, S.-S. Chen, Z.-Y. Han and L.-Z. Gong, Org.
Lett. 2018, 20, 2485. (f) P. A. Sibbald, C. F. Rosewall, R. D.
Swartz and F. E. Michael, J. Am. Chem. Soc. 2009, 131, 15945.
(
g) E. L. Ingalls, P. A. Sibbald, W. Kaminsky and F. E. Michael, J. 17 (a) X. Kou, Y. Li, L. Wu, X. Zhang, G.; Yang and W. Zhang, Org.
Am. Chem. Soc. 2013, 135, 8854.
Lett. 2015, 17, 5566. (b) K. Muñiz, C. H. Hövelmann and J.
Streuff, J. Am. Chem. Soc. 2008, 130, 763.
6
Selected examples on Cu-catalyzed diamination: (a) K. Shen
and Q. Wang, Chem. Sci. 2015, 6, 4279. (b) K. Shen and Q. 18 (a) T. P. Hettinger and L. C. Craig, Biochemistry 1970, 9, 1224.
Wang, J. Am. Chem. Soc. 2017, 139, 13110. (c) W.-B. Cao, X.-
P. Xu and S.-J. Ji, Adv. Synth. Catal. 2019, 361, 1771. (d) M.
Chen, L.-J. Wang, P.-X. Ren, X.-Y. Hou, Z. Fang, M.-N. Han and
W. Li, Org. Lett. 2018, 20, 510. (e) Y. F. Wang, X. Zhu and S.
Chiba, J. Am. Chem. Soc. 2012, 134, 3679. (f) H. Zhang, W. Pu,
T. Xiong, Y. Li, X. Zhou, K. Sun, Q. Liu and Q. Zhang, Angew.
Chem., Int. Ed. 2013, 52, 2529. (g) B. W. Turnpenny and S. R.
Chemler, Chem. Sci. 2014, 5, 1786. (h) T. P. Zabawa, D. Kasi
and S. R. Chemler, J. Am. Chem. Soc. 2005, 127, 11250. (i) R.-
H. Liu, D. Wei, B. Hanand and W. Yu, ACS. Catal. 2016, 6, 6525.
Selected examples on Ni-catalyzed diamination: (a) K. Muñiz,
J. Streuff, C. H. Hövelmann and A. Núñez, Angew. Chem., Int.
Ed. 2007, 46, 7125. (b) M. Chierchia, C. Law and J. P. Morken,
Angew. Chem., Int. Ed. 2017, 56, 11870.
(b) H.-J. Schneider, C. Kasper, V. Palyulin and V. V. Samoshin,
Supramol. Chem. 1997, 8, 225. (c) C. Xu, C.-S. Siu and D. S.
Pasco, Arch. Biochem. Biophy. 1998, 358, 149.
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8
Selected examples on Ir-catalyzed diamination: (a) J. H.
Conway and T. Rovis, J. Am. Chem. Soc. 2018, 140, 135. (b) T.
Rossolini, J. A. Leitch, R. Grainger and D. J. Dixon, Org. Lett.
2
018, 20, 6794. (c) D. Yang, W. Yang, G. Cheng, Y. Li and X. Zuo,
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