Organic Letters
Letter
been studied by many groups. For examples, see ref 5. For selected
recent examples, see: (a) Li, B.; Park, Y.; Chang, S. J. Am. Chem. Soc.
2013, 136, 1125. (b) Wang, H.; Dong, B.; Wang, Y.; Li, J.; Shi, Y. Org.
Lett. 2014, 16, 186. (c) Li, B.; Lee, S.; Shin, K.; Chang, S. Org. Lett.
2014, 16, 2010. (d) Armanino, N.; Lafrance, M.; Carreira, E. M. Org.
Lett. 2014, 16, 572.
no obvious formation of palladium black in the reaction with PGeP-Pd
complex 1b.
(19) We have examined the reaction with a typical PCP-Pd, PNP-Pd,
Pd/DPEphos and common Pd catalysts such as PdCl2(PPh3)2 and
[Pd(π-allyl)Cl]2; however, no product was obtained.
(20) With the PSiP-Pd/AlEt3 system the reaction of mono- and 1,3-
disubstituted allenes gives β,γ-unsaturated carboxylic acid together
with a small amount of its regioisomer and α,β-unsaturated carboxylic
acid as the product. For details, see ref 11.
́
(7) (a) Simonato, J.-P.; Walter, T.; Metivier, P. J. Mol. Catal. A:
Chem. 2001, 171, 91. (b) Simonato, J.-P. J. Mol. Catal. A: Chem. 2003,
197, 61. Porcheddu et al. reported a hydroformylation reaction using
an excess amount of formic acid as a CO source using a two-chamber
system. See: (c) Mura, M. G.; Luca, L. D.; Giacomelli, G.; Porcheddu,
A. Adv. Synth. Catal. 2012, 354, 3180.
1
(21) The 13C-content in H13COONBnMe3 was determined by H
and 13C NMR. The 13C-content in 4a was calculated by EI-MS. See
Supporting Information for details.
(22) For details, see Supporting Information.
(8) (a) Cacchi, S.; Fabrizi, G.; Goggiamani, A. Org. Lett. 2003, 5,
4269. (b) Berger, P.; Bessmernykh, A.; Caille, J.-C.; Mignonac, S.
Synthesis 2006, 3106. (c) Korsager, S.; Taaning, R. H.; Skrydstrup, T. J.
Am. Chem. Soc. 2013, 135, 2891.
(9) Nozaki and co-workers reported the palladium-catalyzed
carboxylation of aromatic C−H bond with excess formic acid;
however, the mechanism has not been made clear yet. (a) Shibahara,
F.; Kinoshita, S.; Nozaki, K. Org. Lett. 2004, 6, 2437. (b) Sakakibara,
K.; Yamashita, M.; Nozaki, K. Tetrahedron Lett. 2005, 46, 959.
(10) For recent reviews on CO2 fixation through C−C bond
formation, see: (a) Huang, K.; Sun, C.-L.; Shi, Z.-J. Chem. Soc. Rev.
2011, 45, 2435. (b) Cokoja, M.; Bruckmeier, C.; Rieger, B.; Herrmann,
W. A.; Fritz E. Kuhn, F. E. Angew. Chem., Int. Ed. 2011, 50, 8510.
̈
(c) Zhang, W.; Lu, X. Chin. J. Catal. 2012, 33, 745. (d) Oame, I. Coord.
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Chem. Rev. 2012, 256, 1384. (e) Tsuji, Y.; Fujihara, T. Chem. Commun.
2012, 48, 9956. (f) Takimoto, M. J. Synth. Org. Chem. Jpn. 2013, 71,
2010. (g) Zhang, L.; Hou, Z. Chem. Sci. 2013, 4, 3395. (h) Cai, X.; Xie,
B. Synthesis 2013, 45, 3305. (i) Johnson, M. T.; Wendt, O. F. J.
Organomet. Chem. 2014, 751, 213. (j) Jonasson, K. J.; Wendt, O. F. In
Pincer and Pincer-Type Complexes: Applications in Organic Synthesis and
Catalysis; Szabo,
2014; pp 213−227. (k) Takaya, J.; Iwasawa, N. In Pincer and Pincer-
Type Complexes: Applications in Organic Synthesis and Catalysis; Szabo,
́
K. J., Wendt, O. F., Eds.; Wiley-VCH: Weinheim,
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K. J., Wendt, O. F., Eds.; Wiley-VCH: Weinheim, 2014; pp 229−248.
(11) (a) Takaya, J.; Iwasawa, N. J. Am. Chem. Soc. 2008, 130, 15254.
(b) Takaya, J.; Sasano, K.; Iwasawa, N. Org. Lett. 2011, 13, 1698.
(12) For recent reports on hydrocarboxylation of unsaturated
hydrocarbons with CO2, see: (a) Williams, C. M.; Johnson, J. B.;
Rovis, T. J. Am. Chem. Soc. 2008, 130, 14936. (b) Fujihara, T.; Xu, T.;
Semba, K.; Terao, J.; Tsuji, Y. Angew. Chem., Int. Ed. 2011, 50, 523.
(c) Li, S.; Yuan, W.; Ma, S. Angew. Chem., Int. Ed. 2011, 50, 2578.
(13) We have reported the synthesis of pincer-type PGeP and PSnP
ligands as well as the corresponding palladium complexes. See: Takaya,
J.; Nakamura, S.; Iwasawa, N. Chem. Lett. 2012, 41, 967.
(14) (a) Mitton, S. J.; Turculet, L. Chem.Eur. J. 2012, 18, 15258.
(b) Suh, H.-W.; Schmeier, T. J.; Hazari, N.; Kemp, R. A.; Takase, M.
K. Organometallics 2012, 31, 8225.
(15) (a) Szabo,
Kjellgren, J.; Szabo,
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K. J. Chem.Eur. J. 2000, 6, 4413. (b) Solin, N.;
́
K. J. J. Am. Chem. Soc. 2004, 126, 7026.
(c) Takaya, J.; Iwasawa, N. Organometallics 2009, 28, 6636. (d) Suh,
H.-W.; Guard, L. M.; Hazari, N. Chem. Sci. 2014, 5, 3859.
(16) Here “a catalytic amount” means that there exists a maximum of
an equimolar amount of CO2 compared to the Pd catalyst in the
reaction medium during the reaction.
(17) Related CO recycling protocols have been reported by Backvall
̈
2
et al. and Yoshida et al. in the Pd-catalyzed decarboxylation of
propargyl- or allylcarbonate derivatives. In these reactions the released
CO2 is captured by a highly reactive anionic oxygen or nitrogen
nucleophile. See: (a) Backvall, J.-E.; Granberg, K. L.; Heumann, A. Isr.
̈
J. Chem. 1991, 31, 17. (b) Yoshida, M.; Ihara, M. Angew. Chem., Int. Ed.
2001, 40, 616. (c) Yoshida, M.; Fujita, M.; Ishii, T.; Ihara, M. J. Am.
Chem. Soc. 2003, 125, 4874. (d) Yoshida, M. Chem. Pharm. Bull. 2012,
60, 285 and references cited therein.
(18) Formation of palladium black was observed in the reaction with
PSiP-Pd complex 1a, which is likely due to the decomposition of the
highly reactive allyl PSiP-Pd intermediate. As a comparison, there was
D
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