E
Synlett
W. Han et al.
Letter
Based on the above results and previous stud-
we proposed a mechanism for the reductive
carbonylation reaction (Scheme 2). Initially, palladium
(2) Schoenberg, A.; Heck, R. F. J. Am. Chem. Soc. 1974, 96, 7761.
ies,5
,10d,12a,13,19
(3) For some recent reviews on Pd-catalyzed carbonylations of aryl
halides, see: (a) Wu, X. F.; Neumann, H.; Beller, M. Chem. Rev.
2
013, 113, 1. (b) Wu, X. F.; Neumann, H.; Beller, M. Chem. Soc.
Rev. 2011, 40, 4986. (c) Grigg, R.; Mutton, S. P. Tetrahedron
010, 66, 5515. (d) Brennführer, A.; Neumann, H.; Beller, M.
nanoparticles are generated in situ from Pd(OAc) and PEG-
2
13,19
4
00.
And then, the nanoparticles undergo oxidative ad-
2
dition of aryl iodide to form ArPdI intermediate, followed by
interception of carbon monoxide to give acylpalladium spe-
cies (ArCOPdI). Finally, the acylpalladium species is reduced
Angew. Chem. Int. Ed. 2009, 48, 4114. (e) Barnard, C. F. J. Organo-
metallics 2008, 27, 5402. (f) Wu, X. F.; Beller, M. Transition Metal
Catalyzed Carbonylation Reactions-Carbonylative Activation of
C–X Bonds; Springer: Berlin, Heidelberg, 2013.
by Et SiH to afford the aldehyde and regenerate the palladi-
3
5,10d,12a
(4) (a) Qi, X. X.; Li, C.-L.; Wu, X. F. Chem. Eur. J. 2016, 22, 5835.
b) Cacchi, S.; Fabrizi, G.; Goggiamani, A. J. Comb. Chem. 2004, 6,
92.
5) Ueda, T.; Konishi, H.; Manabe, K. Angew. Chem. Int. Ed. 2013, 52,
611.
um(0) catalyst.
(
6
CO
(
(
(
(
I
8
6) Korsager, S.; Taaning, R. H.; Lindhardt, A. T.; Skrydstrup, T. J. Org.
Chem. 2013, 78, 6112.
7) Natte, K.; Dumrath, A.; Neumann, H.; Beller, M. Angew. Chem.
Int. Ed. 2014, 53, 10090.
8) Christensen, S. H.; Olsen, E. P. K.; Rosenbaum, J.; Madsen, R. Org.
Biomol. Chem. 2015, 13, 938.
Ar
I
PEG-CHO
ArI
COAr
PEG-OH
Et3SiH
PEG
Pd(OAc)2
Pd(0)
(9) (a) Barnard, C. F. J. Organometallics 2008, 27, 5402. (b) Barnard,
C. F. J. Org. Process Res. Dev. 2008, 12, 566. (c) Maitlis, P. M.;
Haynes, A. Synthesis Based on Carbon Monoxide, In Metal-Cataly-
sis in Industrial Organic Processes; Chiusoli, G. P.; Maitlis, P. M.,
Eds.; RSC Publishing: Cambridge, 2006.
ArCHO + Et3SiI
Scheme 2 Proposed reaction mechanism
(
10) For selected examples of palladium-catalyzed reductive carbon-
ylation of aryl halides, see: (a) Klaus, S.; Neumann, H.; Zapf, A.;
Strubing, D.; Huber, S.; Almena, J.; Riermeier, T.; Gross, P.;
Sarich, M.; Krahnert, W.-R.; Rossen, K.; Beller, M. Angew. Chem.
Int. Ed. 2005, 45, 154. (b) Hamasaki, A.; Yasutaka, Y.; Norio, T.;
Ishida, T.; Akita, T.; Ohashi, H.; Yokoyama, T.; Honma, T.;
Tokunaga, M. Appl. Catal., A 2014, 469, 146. (c) Hao, W. Y.; Ding,
G. D.; Cai, M. Z. Catal. Commun. 2014, 51, 53. (d) Sergeev, A. G.;
Spannenberg, A.; Beller, M. J. Am. Chem. Soc. 2008, 130, 15549.
In summary, a facile and robust method has been
demonstrated for reductive carbonylation of aryl iodides to
provide aromatic aldehydes in high yields with high selec-
tivities. Noteworthy is that the transformation is conducted
under ambient temperature and pressure and even in the
absence of an added ligand. In addition, the double reduc-
tive carbonylation of diiodobenzenes, which is sparsely re-
ported, can be achieved in our catalytic system. Advanta-
geously, the catalytic system is in situ generated, which ob-
viate cumbersome processes for the preparation of metal
nanoparticles, and can be recyclable. Control experiments
suggest that a typical heterogeneous reaction process is un-
likely to be in operation.
(e) Brennführer, A.; Neumann, H.; Beller, M. Synlett 2007, 2537.
(f) Carelli, I.; Chiarotto, I.; Cacchi, S.; Pace, P.; Amatore, C.;
Jutand, A.; Meyer, G. Eur. J. Org. Chem. 1999, 1471. (g) Hamasaki,
A.; Yasutaka, Y.; Norio, T.; Ishida, T.; Akita, T.; Ohashi, H.;
Yokoyama, T.; Honma, T.; Tokunaga, M. Appl. Catal., A 2014, 469,
146. (h) Neumann, H.; Kadyrov, R.; Wu, X. F.; Beller, M. Chem.
Asian J. 2012, 7, 2213. (i) Singh, A. S.; Bhanage, B. M.; Nagarkar, J.
M. Tetrahedron Lett. 2011, 52, 2383. (j) Brennführer, A.;
Neumann, H.; Klaus, S.; Riermeier, T.; Almena, J.; Beller, M. Tet-
rahedron 2007, 63, 6252. (k) Yu, B.; Yang, Z. Z.; Zhao, Y. F.; Hao,
L. D.; Zhang, H. Y.; Gao, X.; Han, B. X.; Liu, Z. M. Chem. Eur. J.
2016, 22, 1097. (l) Yu, B.; Zhao, Y. F.; Zhang, H. Y.; Xu, J. L.; Hao,
L. D.; Gao, X.; Liu, Z. M. Chem. Commun. 2014, 50, 2330.
Acknowledgment
The work was sponsored by the Natural Science Foundation of Jiangsu
Province (BK20161553), the Natural Science Foundation of China
(21302099), the Natural Science Foundation of Jiangsu Provincial Col-
leges and Universities (16KJB150019), the SRF for ROCS, SEM, the
Qing Lan project, and the Priority Academic Program Development of
Jiangsu Higher Education Institutions
(11) (a) Zhao, H. Y.; Du, H. Y.; Yuan, X. R.; Wang, T. J.; Han, W. Green
Chem. 2016, 18, 5782. (b) Zhong, Y. Z.; Han, W. Chem. Commun.
2014, 50, 3874. (c) Zhou, Q.; Wei, S. H.; Han, W. J. Org. Chem.
2014, 79, 1454. (d) Han, W.; Jin, F. L.; Zhou, Q. Synthesis 2015,
47, 1861. (e) Zhong, Y. Z.; Gong, X. X.; Zhu, X. S.; Ni, Z. C.; Wang,
Supporting Information
H. Y.; Fu, J. L.; Han, W. RSC Adv. 2014, 4, 63216. (f) Cheng, L. J.;
Zhong, Y. Z.; Ni, Z. C.; Du, H. Y.; Jin, F. L.; Rong, Q.; Han, W. RSC
Adv. 2014, 4, 44312.
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0036-1588930.
S
u
p
p
ortioIgnfrm oaitn
S
u
p
p
ortioIgnfrm oaitn
(
12) For silanes as hydride source for reductive carbonylation of aryl
halides, see: (a) Ashfield, L.; Barnard, C. F. J. Org. Process Res. Dev.
2
4
4
007, 11, 39. (b) Pri-Bar, I.; Buchman, O. J. Org. Chem. 1984, 49,
009. (c) Kotsuki, H.; Datta, P. K.; Suenaga, H. Synthesis 1996,
70.
References and Notes
(1) Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry;
(
13) Palladium nanoparticles were prepared according to the refer-
Springer: Heidelberg, 2007.
ence: Han, W.; Liu, C.; Jin, Z. L. Adv. Synth. Catal. 2008, 350, 501.
©
Georg Thieme Verlag Stuttgart · New York — Synlett 2017, 28, A–F