Palladium-catalyzed oxidative carbonylation of hydrazides: Synthesis of 1,3,4-oxadiazol-2(3H)-ones

Article abstract of DOI:10.1039/c4cc08731c

A novel palladium-catalyzed oxidative carbonylation reaction was developed via the carbon monoxide insertions between the amine group and the carbonyl group to realize the intramolecular cyclization, which provides efficient access to 1,3,4-oxadiazol-2(3H)-ones with a wide range of substrates under mild conditions, resulting in good to excellent yields.

Full text of DOI:10.1039/c4cc08731c

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Palladium-catalyzed oxidative carbonylation of
hydrazides: synthesis of 1,3,4-oxadiazol-2(3H)-ones†
Cite this:DOI: 10.1039/c4cc08731c
Yu Wang,ab Xu Meng,c Yuting Yang,ab Lutao Zhang,ab Shuaibo Guo,ab Dong Tang,ab
Yaxuan Liab and Baohua Chen*ab
Received 3rd November 2014,
Accepted 6th December 2014
DOI: 10.1039/c4cc08731c
www.rsc.org/chemcomm
A novel palladium-catalyzed oxidative carbonylation reaction was in palladium-catalyzed oxidative carbonylations, respectively
developed via the carbon monoxide insertions between the amine (Scheme 1a and b),11,12 no example has been reported on the CO
group and the carbonyl group to realize the intramolecular cycliza- insertion between these two nucleophiles for the intramolecular
tion, which provides efficient access to 1,3,4-oxadiazol-2(3H)-ones cyclocarbonylation. Encouraged by previous work, we aimed to
with a wide range of substrates under mild conditions, resulting in synthesize 1,3,4-oxadiazol-2(3H)-ones by using a more straight-
good to excellent yields.
forward method under mild conditions. Hence, we develop a
convenient Pd-catalyzed oxidative cyclocarbonylation of hydr-
Since the work pioneered by Heck and co-workers in 1974,1 azides via the CO insertions between the amine group and the
transition-metal-catalyzed carbonylation has been recognized as carbonyl group for the formation of 1,3,4-oxadiazol-2(3H)-ones
an efficient and straightforward method to synthesize carbonyl (Scheme 1c), which could be considered as an environmentally
derivatives,2 which increases the carbon number and is in agree- friendly approach to these species.2b,5b,c
ment with the green chemistry principle at the same time.3
Evaluation of this palladium-catalyzed CO insertion strategy
However, transition-metal-catalyzed carbonylations are performed began with the exposure of benzoyl 2-phenylhydrazide to a series
in high CO pressure and at relatively high temperature.4 Therefore, of palladium catalysts under a CO atmosphere (Table 1). Unfor-
the oxidative carbonylation of CO has increasingly become an tunately, the reaction failed to provide the desired product 2a in
efficient solution to meet these harsh and inaccessible conditions.5 the presence of PdCl2 (Table 1, entries 1 and 2). In the screening
In addition, the carbonylated derivatives, instead of using R–X of Pd-catalysts, including Pd(PPh3)2Cl2, [PdCl2(dppf)]CH2Cl2
as the electrophiles which are prepared from the corresponding and Pd(OAc)2, [PdCl2(dppf)]CH2Cl2 showed good activity for
nucleophiles to realize the carbonylation, can be obtained from this transformation and a 46% product yield of 2a was obtained
two nucleophiles with the assistance of oxidants which are used (Table 1, entries 3–5). As expected, with PdCl2 and Pd(OAc)2 as
in oxidative carbonylations.5c,6
The 1,3,4-oxadiazol-2(3H)-one core is an important scaffold
found in medicinal chemistry, which is widely used as a hormone-
sensitive lipase (HSL) inhibitor,7 a herbicide, a fungicide,8 and a
function tool in chemical science.9 Thus, various methods were
developed for the synthesis of 1,3,4-oxadiazol-2(3H)-ones involving
the participation of propylene oxide, carbonic dichloride and
phenanthrenequinones.10 To the best of our knowledge, although
amine groups and carbonyl groups are frequently used as nucleophiles
a State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou,
Gansu 730000, P. R. China
b Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu
Province, Lanzhou 730000, P. R. China. E-mail: chbh@lzu.edu.cn;
Fax: +86-931-891-2582
c State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute
of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China
Scheme 1 Carbonylation cyclizations via nucleophiles (amine groups and
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
carbonyl groups).
c4cc08731c
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Table 1 Optimization of the reaction conditionsa
Yieldb
Additive [%]
Entry Catalyst
Ligand
Oxidant
CuCl2
1
2
3
4
PdCl2
PdCl2
Pd(PPh3)2Cl2
[PdCl2(dppf)]- —
CH2Cl2
—
—
—
—
Nd
Trace
33
Cu(OAc)2ÁH2O —
Cu(OAc)2ÁH2O —
Cu(OAc)2ÁH2O —
46
5
6
7
8
9
10
11
Pd(OAc)2
PdCl2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
—
dppf
dppf
1,10-Phen
X-Phos
XantPhos
Cu(OAc)2ÁH2O —
Cu(OAc)2ÁH2O —
Cu(OAc)2ÁH2O —
Cu(OAc)2ÁH2O —
Cu(OAc)2ÁH2O —
Cu(OAc)2ÁH2O —
Trace
21
61
Trace
26
Trace
23
Tri(1-naphthyl)- Cu(OAc)2ÁH2O —
phosphine
12
Pd(OAc)2
Tri(3-tolyl)-
phosphine
dppf
dppf
dppf
dppf
dppf
dppf
dppf
Cu(OAc)2ÁH2O —
Trace
13
14
15
16
17
18
19
20
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
CuCl2
K2S2O4
AgOAc
CuO
—
—
—
—
Nd
Nd
25
Nd
Cu(OAc)2ÁH2O NaOPiv 73
Cu(OAc)2ÁH2O KI
29
Cu(OAc)2ÁH2O NaOAc 75a/57c
dppf
Cu(OAc)2ÁH2O KOAc
35
a
Reaction conditions: hydrazide 1a (0.2 mmol), catalyst (10 mol%), ligand
(20 mol%), oxidant (1 equiv.), additive (1 equiv.), toluene (2 mL), at 80 1C
b
c
under a CO atmosphere (balloon pressure). Isolated yields. Pd(OAc)2
(5 mol%) and dppf (10 mol%) were used as the catalyst and the ligand.
catalysts, the yield of 2a was improved to 21% and 61% when dppf
was added as a ligand (Table 1, entries 6 and 7). Various ligands,
such as 1,10-Phen, X-Phos, XantPhos, Tri(1-naphtyl)phosphine, and
Tri(3-tolyl)phosphine, were also tested and dppf was found to be
the most effective ligand (Table 1, entries 8–12). Meanwhile, better
results were not observed when other oxidants were employed
including CuCl2, K2S2O4, AgOAc, and CuO (Table 1, entries 13–16).
The effect of additives (such as NaOPiv, KI, NaOAc, and KOAc) was
Scheme 2 Palladium-catalyzed carbonylation reaction of hydrazides 1.
Reaction conditions: 1 (0.2 mmol), Pd(OAc)2 (10 mol%), Cu(OAc)2ÁH2O
(1.0 equiv.), CO balloon (1 atm), PhMe (2.0 mL), 80 1C, isolated yields of 2,
for 36 h.
studied, and to our delight NaOAc showed improvement of the N-phenylhydrazide, N-tert-butyl benzoylhydrazide and N-benzyl
palladium-catalyzed carbonylation, thus giving 2a in 75% yield12f,13 benzoylhydrazide were totally inactive to this reaction.
(Table 1, entries 17–20).
Based on previous reports as well as our results,11,12,14
a
With the optimized reaction conditions in hand, we then possible mechanism for this carbonylation is proposed as out-
extended the reaction to a range of substrates. A wide variety of lined in Scheme 3. With the assistance of the carbonyl group of
substitution patterns and functionalities were tolerated, as shown in 1a, its N–H activation by Pd(OAc)2 forms the intermediate A.15
Scheme 2. According to the results, benzoyl 2-phenylhydrazide sub- Insertion of a coordinated CO into the N–Pd bond affords the
stituted with electron-withdrawing groups (2h–j, 2l–o) proceeded intermediate B. The formation of the palladacycle C occurred via
efficiently in good to excellent yields (50–96%). It was worth mention- the release of HOAc. Subsequently, reductive elimination of C
ing that this reaction was compatible with various functional groups provides the desired product 2a and Pd0 species is reoxidized to
such as halogens (F, Cl, and Br) and cyano (2h–j, 2m–n), which could the Pd(II) catalyst. The dppf ligand likely promotes the reductive
be subjected to further synthetic transformation. On the other hand, elimination of Pd(II) from palladacycle C due to the wide bite
hydrazide substitutions with electron-donating groups reacted angle of bis-phosphine.16
smoothly and presented the corresponding products (2b–g, 2k) in
In summary, a highly efficient palladium-catalyzed carbonyla-
46–74% yields. However, to our disappointment, N-acetyl benzoyl- tion of hydrazides for the synthesis of 1,3,4-oxadiazol-2(3H)-ones
hydrazide and benzoyl hydrazine failed to provide the desired was developed, which takes place smoothly under atmospheric
products 2q–r. Unfortunately, 1-acetyl-2-phenylhydrazine, styryl pressure of CO. This is the first example of using both an amine
N-phenylhydrazide, phenylethynyl N-phenylhydrazide, 4-hydroxy-phenyl group and a carbonyl group within one molecule as the two
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4 (a) C. F. J. Barnard, Org. Process Res. Dev., 2008, 12, 566; (b) C. F. J.
Barnard, Organometallics, 2008, 27, 5402.
5 (a) B. Gabriele, R. Mancuso and G. Salerno, Eur. J. Org. Chem., 2012,
6825; (b) Q. Liu, G. Li, J. He, J. Liu, P. Li and A. Lei, Angew. Chem., Int.
Ed., 2010, 49, 3371; (c) Q. Liu, H. Zhang and A. Lei, Angew. Chem., Int.
Ed., 2011, 50, 10788.
6 (a) B. Gabriele, G. Salerno, M. Costa and G. P. Chiusoli, Curr. Org.
Chem., 2004, 8, 919; (b) B. Gabriele, G. Salerno and M. Costa, Top.
Organomet. Chem., 2006, 18, 239.
7 F. Ben Ali, R. Verger, F. Carriere, S. Petry, G. Muller and
A. Abousalham, Biochimie, 2012, 94, 137.
8 (a) H. Chen, Z. Li and Y. Han, J. Agric. Food Chem., 2000, 48, 5312;
(b) L. Jiang, Y. Tan, X. Zhu, Z. Wang, Y. Zuo, Q. Chen, Z. Xi and
G. Yang, J. Agric. Food Chem., 2010, 58, 2643.
9 (a) P. P. Kattimani, R. R. Kamble, M. Y. Kariduraganavar, A. Dorababu
and R. K. Hunnur, Eur. J. Med. Chem., 2013, 62, 232; (b) D. Begue,
A. Dargelos, H. M. Berstermann, K. P. Netsch, P. Bednarek and
C. Wentrup, J. Org. Chem., 2014, 79, 1247; (c) J. L. Romine, S. W.
Martin, N. A. Meanwell, V. K. Gribkoff, C. G. Boissard, S. I. Dworetzky,
J. Natale, S. Moon, A. Ortiz, S. Yeleswaram, L. Pajor, Q. Gao and
J. E. Starrett, J. Med. Chem., 2007, 50, 528.
10 (a) X. Yan, S. Zhou, Y. Wang, Z. Ge, T. Cheng and R. Li, Tetrahedron,
˜
2012, 68, 7978; (b) L. E. Kiss, H. S. Ferreira, A. Beliaev, L. Torrao,
´
M. J. Bonifacio and D. A. Learmonth, MedChemComm, 2011, 2, 889;
Scheme 3 Proposed mechanism for the reaction.
(c) B. Batanero, F. Barba and A. Martin, J. Org. Chem., 2013, 78, 9477.
11 (a) Y. Kondo, F. Shiga, N. Murata, T. Sakamoto and H. Yamanaka,
Tetrahedron, 1994, 50, 11803; (b) B. Gabriele, P. Plastina, G. Salerno and
M. Costa, Synlett, 2005, 935; (c) Y. Tamaru, M. Hojo, H. Higashimura
and Z. Yoshida, J. Am. Chem. Soc., 1988, 110, 3994; (d) E. J. Yoo, M. Wasa
and J. Yu, J. Am. Chem. Soc., 2010, 132, 17378; (e) B. Ma, Y. Wang, J. Peng
and Q. Zhu, J. Org. Chem., 2011, 76, 6362; ( f ) K. Okuro, H. Kai and
H. Alper, Tetrahedron: Asymmetry, 1997, 8, 2307; (g) J. C. Knight,
R. Prabaharan, B. D. Ward, A. J. Amoroso, P. G. Edwards and
B. M. Kariuki, Dalton Trans., 2010, 39, 10031; (h) Q. Liu, G. Li, J. He,
J. Liu, P. Li and A. Lei, Angew. Chem., Int. Ed., 2010, 49, 3371; (i) D. Liang,
Y. He and Q. Zhu, Org. Lett., 2014, 16, 2748; ( j) Z. H. Guan, M. Chen and
Z. H. Ren, J. Am. Chem. Soc., 2012, 134, 17490.
nucleophiles in a CO insertion cyclization reaction, for which
further investigation is currently underway.
Our gratitude goes to the National Nature Science Founda-
tion of China (No. 21372102 and 21403256) who sponsored the
project.
Notes and References
1 (a) R. F. Heck and D. S. Breslow, J. Am. Chem. Soc., 1963, 85, 2779;
(b) A. Schoenberg and R. F. Heck, J. Org. Chem., 1974, 39, 3327.
2 (a) T. L. Church, Y. D. Getzler, C. M. Byrne and G. W. Coates, Chem.
Commun., 2007, 657; (b) X.-F. Wu, H. Neumann and M. Beller, Chem. Rev.,
2013, 113, 1; (c) A. Zapf and M. Beller, Chem. Commun., 2005, 431;
(d) L. Wu, X. Fang, Q. Liu, R. Jackstell, M. Beller and X.-F. Wu, ACS Catal.,
2014, 4, 2977; (e) X.-F. Wu, X. Fang, L. Wu, R. Jackstell, H. Neumann and
M. Beller, Acc. Chem. Res., 2014, 47, 1041; ( f ) X.-F. Wu, H. Neumann and
M. Beller, ChemSusChem, 2013, 6, 229; (g) X.-F. Wu and H. Neumann,
ChemCatChem, 2012, 4, 447; (h) X.-F. Wu, H. Neumann and M. Beller,
Chem. Soc. Rev., 2011, 40, 4986; (i) M. Beller and X.-F. Wu, Transition Metal
Catalyzed Carbonylation Reactions: Carbonylative Activation of C-X Bonds,
Springer, Amsterdam, 2013.
12 (a) K. Okuro, M. Furuune, M. Miura and M. Nomura, J. Org. Chem.,
1992, 57, 4754; (b) K. Kato, T. Mochida, H. Takayama, M. Kimura,
H. Moriyama, A. Takeshita, Y. Kanno, Y. Inouye and H. Akita,
´
Tetrahedron Lett., 2009, 50, 4744; (c) N. Della Ca, F. Campanini,
B. Gabriele, G. Salerno, C. Massera and M. Costa, Adv. Synth. Catal.,
2009, 351, 2423; (d) A. C. Tadd, M. R. Fielding and M. C. Willis,
Chem. Commun., 2009, 6744; (e) C. E. Houlden, M. Hutchby,
´
C. D. Bailey, J. G. Ford, S. N. G. Tyler, M. R. Gagne, G. C. Lloyd-
Jones and K. I. Booker-Milburn, Angew. Chem., Int. Ed., 2009,
48, 1830; ( f ) R. Giri, J. K. Lam and J.-Q. Yu, J. Am. Chem. Soc.,
2010, 132, 686; (g) M. Chen, Z. H. Ren, Y. Y. Wang and Z. H. Guan,
Angew. Chem., Int. Ed., 2013, 52, 14196; (h) L. Troisi, C. Granito,
S. Perrone and F. Rosato, Tetrahedron Lett., 2011, 52, 4330.
13 R. Giri and J.-Q. Yu, J. Am. Chem. Soc., 2008, 130, 14082.
14 V. L. K. Valli and H. Alper, Organometallics, 1995, 14, 80.
15 T. Fang, Q. Tan, Z. Ding, B. Liu and B. Xu, Org. Lett., 2014, 16, 2342.
16 C. Larksarp and H. Alper, J. Org. Chem., 2000, 65, 2773.
3 (a) R. A. Sheldon, Green Chem., 2007, 9, 1273; (b) J. J. Song, J. T. Reeves,
D. R. Fandrick, Z. Tan, N. K. Yee and C. H. Senanayake, Green Chem. Lett.
Rev., 2008, 1, 141; (c) S. Tang, R. Bourne, R. Smith and M. Poliakoff,
Green Chem., 2008, 10, 268; (d) P. Anastas and N. Eghbali, Chem. Soc.
Rev., 2010, 39, 301.
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