Organic & Biomolecular Chemistry
Communication
experimental observation shown in Table 1, entry 8. The
absence of Cu salt did not result in the desired catalytic cycle.
Among the Cu salts, Cu(OAc)2 was the most effective in terms
of selectivity obtaining the desired product. This indicated
that acetate ion was effective in terms of modulating the equili-
brium of transfer vinylation.9a–e,10 Acetal (4c) was a minor by-
product in each reaction.
5 (a) K. C. Nicolaou, S. A. Snyder, T. Montagnon and
G. Vassilikogiannakis, Angew. Chem., Int. Ed., 2002, 41,
1668; (b) S. K. Chittimalla, H. Shiao and C. Liao, Org.
Biomol. Chem., 2006, 4, 2267.
6 S. Liu, N. Berry, N. Thomson, A. Pettman, Z. Hyder, J. Mo
and J. Xiao, J. Org. Chem., 2006, 71, 7467.
7 (a) A. Kanazawa, S. Kanaoka and S. Aoshima, Chem. Lett.,
2010, 39, 1232; (b) H. Mokbel, F. Dumur, C. R. Mayer,
F. Morlet-Savary, B. Graff, D. Gigmes, J. Toufaily,
T. Hamieh, J. Fouassier and J. Lalevée, Dyes Pigm., 2014,
105, 121; (c) V. Kottisch, Q. Michaudel and B. P. Fors, J. Am.
Chem. Soc., 2016, 138, 15535; (d) S. Sugihara, A. Yoshida,
S. Fujita and Y. Maeda, Macromolecules, 2017, 50, 8346;
(e) S. Zouganelis, I. Choinopoulos, I. Goulas and
M. Pitsikalis, Polymers, 2019, 11, 1510; (f) D. Xie and Y. Lu,
Eur. Polym. J., 2019, 113, 220; (g) E. Kirillov, K. Rodygin and
V. Ananikov, Eur. Polym. J., 2020, 136, 109872.
8 W. Reppe, Justus Liebigs Ann. Chem., 1956, 601, 84.
9 Pd: (a) P. M. Weintraub and C.-H. R. King, J. Org. Chem.,
1997, 62, 1560; (b) S. Handerson and M. Schlaf, Org. Lett.,
2002, 4, 407; (c) M. Bosch and M. Schlaf, J. Org. Chem.,
2003, 68, 5225; (d) L. Pichavant, C. Guillermain and
X. Coqueret, Biomacromolecules, 2010, 11, 2415;
(e) A. Alaaeddine, G. Couture and B. Ameduri, Polym.
Chem., 2013, 4, 4335; Ir: (f) Y. Okimoto, S. Sakaguchi and
Y. Ishii, J. Am. Chem. Soc., 2002, 124, 1590; Au:
(g) A. Nakamura and M. Tokunaga, Tetrahedron Lett., 2008,
49, 3729; Hg: (h) W. H. Watanabe and L. E. Conlon, J. Am.
Chem. Soc., 1957, 79, 2828.
10 (a) J. E. McKeon, P. Fitton and A. A. Griswold, Tetrahedron,
1972, 28, 227; (b) J. E. McKeon and P. Fitton, Tetrahedron,
1972, 28, 233.
11 (a) J. Dupont and J. D. Scholten, Chem. Soc. Rev., 2010, 39,
1780; (b) A. Chen and C. Ostrom, Chem. Rev., 2015, 115,
11999; (c) I. Chakraborty and T. Pradeep, Chem. Rev., 2017,
117, 8208; (d) J. He, S. Li, D. Lyu, D. Zhang, X. Wu and
Q. Xu, Mater. Chem. Front., 2019, 3, 2421.
12 (a) A. Roucoux, J. Schulz and H. Patin, Chem. Rev., 2002,
102, 3757; (b) L. Liu and A. Corma, Chem. Rev., 2018, 118,
4981; (c) J. M. Asensio, D. Bouzouita, P. W. N. M. van
Leeuwen and B. Chaudret, Chem. Rev., 2020, 120, 1042;
(d) S. Gong, Y. Zhang and Z. Niu, ACS Catal., 2020, 10,
10886.
Based on the experimental work and previous reports,9a–e,10
Fig. S2† shows a plausible reaction mechanism. Starting from
a Pd species, which has an acetoxy group supplied from Cu
(OAc)2 or an alkoxy group supplied from an alcohol through an
oxidative pathway of the Pd species, coordination of vinyl ether
to the Pd species generates a Pd alkene species (l). The attack
of the alcohol forms a Pd alkyl intermediate (lI). The corres-
ponding vinyl ether is obtained via β-alkoxy elimination. The
DMF molecules would be strongly surrounding the coordi-
nation environment of Pd in the catalyst system, and the DMF
molecules would assist as a stabiliser and prevent the Pd NPs
from aggregation during the reaction course.14
In conclusion, we report DMF-stabilised, Pd NP-catalysed
transfer vinylation of alcohols from vinyl ether. The one-step-
synthesised Pd NPs are recyclable in this catalytic system. The
observation of Pd NPs by DLS and TEM analyses indicate that
Cu(OAc)2 and bathophenanthroline prevent deleterious aggre-
gation of the Pd NPs in n-butyl vinyl ether.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was partly supported by JSPS KAKENHI Grant
Number 19K05573. We thank Mr Yosuke Murakami and Mr
Takeshi Ishibashi of the Comprehensive Analysis Center,
SANKEN (ISIR), Osaka University, for performing TEM ana-
lyses. High-resolution mass spectra were recorded at the
Global Facility Center, Hokkaido University.
Notes and references
1 (a) D. J. Winternheimer, R. E. Shade and C. A. Merlic,
Synthesis, 2010, 2497; (b) K. Minami, Y. Kawamura, K. Koga 13 (a) H. Kawasaki, H. Yamamoto, H. Fujimori, R. Arakawa,
and T. Hosokawa, Org. Lett., 2005, 7, 5689; (c) Y. Kawamura,
Y. Kawano, T. Matsuda, Y. Ishitobi and T. Hosokawa, J. Org.
Chem., 2009, 74, 3048; (d) Z. Zhu and S. F. Kirsch, Chem.
Commun., 2013, 49, 2272; (e) Q. Deng, L. Tan, Y. Xu, P. Liu
and P. Sun, J. Org. Chem., 2018, 83, 6151.
Y. Iwasaki and M. Inada, Langmuir, 2010, 26, 5926;
(b) H. Kawasaki, H. Yamamoto, H. Fujimori, R. Arakawa,
M. Inada and Y. Iwasaki, Chem. Commun., 2010, 46, 3759;
(c) H. Kawasaki, Nanotechnol. Rev., 2013, 2, 5; (d) T. Nagata
and Y. Obora, ACS Omega, 2020, 5, 98.
2 T. H. Fife, J. Am. Chem. Soc., 1965, 87, 1084.
14 (a) M. Hyotanishi, Y. Isomura, H. Yamamoto, H. Kawasaki
and Y. Obora, Chem. Commun., 2011, 47, 5750; (b) H. Yano,
Y. Nakajima and Y. Obora, J. Organomet. Chem., 2013, 745,
258; (c) S. Asada, A. Nito, Y. Miyagi, J. Ishida, Y. Obora and
F. Sanda, Macromolecules, 2017, 50, 4083; (d) K. Onishi,
K. Oikawa, H. Yano, T. Suzuki and Y. Obora, RSC Adv.,
2018, 8, 11324; (e) T. Nagata, T. Inoue, X. Lin, S. Ishimoto,
3 (a) R. K. Boeckman, M. d. R. R. Ferreira, L. H. Mitchell and
P. Shao, J. Am. Chem. Soc., 2002, 124, 190; (b) X. Wei,
J. C. Lorenz, S. Kapadia, A. Saha, N. Haddad, C. A. Busacca
and C. H. Senanayake, J. Org. Chem., 2007, 72, 4250.
4 Y. Terada, M. Arisawa and A. Nishida, Angew. Chem., Int.
Ed., 2004, 43, 4063.
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