10.1002/chem.201905199
Chemistry - A European Journal
COMMUNICATION
[2]
a) A. D. Abell, M. K. Edmonds, in: Organophosphorus Reagents, (Ed.:
P. J. Murphy), Oxford, UK, 2004, 99; b) A. Maercker, The Wittig
Reaction, Organic Reactions, 2011, 270; c) B. E. Maryanoff, A. B. Reitz,
Chem. Rev. 1989, 89, 863-927; d) R. W. Hoffmann, Angew. Chem. Int.
Ed. 2001, 40, 1411-1416; Angew. Chem. 2001,113, 1457-1462.
Reviews on olefin metathesis: a) A. H. Hoveyda, A. R. Zhugralin,
Nature 2007, 450, 243-251; b) G. C. Vougioukalakis, R. H. Grubbs,
Chem. Rev. 2010, 110, 1746-1787.
CO2Et
Δν αξαξ Οξα ανα
Ph
Cl3Au
CO 2Et
Ph
H
Cl3Au
O
Ph
O
Cl3Au
CO2Et
O
H
TS2
H
[3]
[4]
23.9
(14.2)
(20.0)
TS3
TS1
Ph
INT1
CO2Et
Cl3Au
18.5
(22.9)
(8.2)
16.1
O
14.2
(unstable)
(4.9)
(11.6)
+ AuCl3
(35.3)
a) H. Renata, K. M. Engle in Applications of Domino Transformations in
Organic Synthesis 1 (Ed.: S. A. Snyder), Thieme, 2016, 116-137; b) E.
T. Hennessy, E. N. Jacobsen, Nat. Chem. 2016, 8, 741-742.
Cl3Au
H
1a
O
Ph
O
Cl3Au
CO2Et
0
(0)
oxetane
O
-4.4
(0.13)
(-16.8)
+
[5] a) T. Takeda, A. Tsubouchi. Carbonyl Olefination Utilizing Metal Carbene
Complexes, In Modern Carbonyl Olefination; Takeda, T., Ed.; Wiley-
VCH: Weinheim, 2004, 151-199; b) A. Dauth, J. A. Love. Chem. Rev.
2011, 111, 2010-2047.
CO2Et
(-24.5)
Ph
Ph
H
CO2Et
2a
[6]
For excellent examples about non-catalytic approaches: a) O. Meresz,
K.P. Leung, A.S. Denes. Tetrahedron Lett. 1972, 13, 2797-2800; b) G.
II. Jones, S. B. Schwartz, M. T. Marton. J. Chem. Soc., Chem.
Commun. 1973, 374-375; c) G. Jones II, M. A. Acquadro, M. A.
Carmody, J. Chem. Soc., Chem. Commun., 1975, 6, 206-207; d) H. A.
J. Carless, H. Trivedi. J. Chem. Soc., Chem. Commun. 1979, 382-383;
e) T. Imai, S. Nishida. Can. J. Chem. 1981, 59, 2503-2509; f) Bach, T.
Synthesis 1998, 683-703; g) R. A. Valiulin, A. G. Kutateladze. Org.
Lett., 2009, 11, 3886–3889; h) M. D’Auria, R. Racioppi, L. Viggiani.
Photochem. Photobiol. Sci. 2010, 9, 1134-1138.
-31.1 (-38.0)
Scheme 2. DFT calculations for metathesis reaction catalyzed by AuCl3, the
free energies in the parentheses are the pathway in the presence of GaCl3 and
BiCl3, respectively.
In conclusion, we have successfully developed a mild AuCl3-
catalyzed intramolecuar ring-colsing carbonyl−olefin metathesis
reaction providing target cyclopentenes, polycycles and N-
heterocycles derivatives in good to excellent yields, especially
this method offers a facile entry to benzocarbocycles through
intramolecuar ring-colsing aldehyde–olefin metathesis. This
method features easily accessible starting materials, simple
operation, broad substrate scope, good functional group
tolerance and short reaction time. All of these combined with
the importance of target molecule make this new method a
useful advancement for recent reports about carbonyl−olefin
metathesis reaction and paradigms in retrosynthetic analysis of
complex molecules. Further studies on extending the use of the
methodology to macrocycles are underway.
[7]
[8]
For reviews see: a) C. Schindler, J. Ludwig, Synlett 2017, 28, 1501-
1509; b) L. Ravindar, R. Lekkala, K. Rakesh, A. M. Asiri, H. M. Marwani,
H.-L. Qin, Org. Chem. Front. 2018, 5, 1381-1391; c) M. R. Becker, R. B.
Watson, C. S. Schindler. Chem. Soc. Rev. 2018, 47, 7867−7881; d) E.
J. Groso, C. S. Schindler. Synthesis 2019, 51, 1100−1114.
a) A. K. Griffith, C. M. Vanos, T. H. Lambert, J. Am. Chem. Soc. 2012,
134, 18581-18584; b) A.-L. Lee, Angew. Chem. Int. Ed. 2013, 52, 4524-
4525; c) X. Hong, Y. Liang, A. K. Griffith, T. H. Lambert, K. N. Houk,
Chem. Sci. 2014, 5, 471-475. Recent application for hydrazine-
catalyzed carbonyl-olefin metathesis: d) Y. Zhang, J. Jermaks, S. N.
MacMillan, T. H. Lambert. ACS Catal. 2019, 9, 9259−9264.
[9]
a) J. R. Ludwig, P. M. Zimmerman, J. B. Gianino, C. S. Schindler,
Nature 2016, 533, 374-379; b) L. Ma, W. Li, H. Xi, X. Bai, E. Ma, X. Yan,
Z. Li, Angew. Chem. Int. Ed. 2016, 55, 10410-10413; Angew. Chem.
2016, 128, 10566-10569; c) C. C. McAtee, P. S. Riehl, C. S. Schindler,
J. Am. Chem. Soc. 2017, 139, 2960-2963; d) J. R. Ludwig, S. Phan, C.
C. McAtee, P. M. Zimmerman, J. J. Devery, Schindler, C. S. J. Am.
Chem. Soc. 2017, 139, 10832-10842; e) E. J. Groso, A. N. Golonka, R.
A. Harding, B. W. Alexander, T. M. Sodano, C. S. Schindler, ACS Catal.
2018, 8, 2006-2011; f) J.R. Ludwig, R. B. Watson, D. J. Nasrallah, J. B.
Gianino, P. M. Zimmerman, R. A. Wiscons, C. S. Schindler, Science
2018, 361, 1363-1369; g) H. Albright, P. S. Riehl, C. C. McAtee, J. P.
Reid, J. R. Ludwig, L. Karp, P. M. Zimmerman, M.S Sigman, C. S.
Schindler, J. Am. Chem. Soc. 2019, 141, 1690-1700.
Acknowledgements
We gratefully acknowledge support from CSTC (2015jcyjA90023,
2015jcyjBX0080), the Innovative Research Team Development
Program in University of Chongqing (No. cxtdx201601031), and
the Scientific and Technological Research Program of
Chongqing Municipal Education Commission (KJ1600906,
KJZD-K201801102) for financial support.
[10] a) U. P. N. Tran, G. Oss, D. P. Pace, J. Ho, T. V. Nguyen, Chemical
Science, 2018, 9, 5145-5151; b) S. Ni, J. Franzén, Chem. Commun.
2018, 54, 12982-12985; c) V. R Naidu, J. Bah, J. Franzen, Eur. J. Org.
Chem. 2015, 8, 1834-1839; d) V.
R Naidu, S. Ni, J. Franzen,
Keywords: Catalytic carbonyl–olefin Metathesis • gold catalysis•
ChemCatChem 2015, 7, 1896-1905; e) A. Soicke, N. Slavov, J.-M.
Neudörfl, H.-G. Schmalz, Synlett 2011, 17, 2487-2490; f) C. Jossifov, R.
Kalinova, A. Demonceau, Chim. Oggi 2008, 26, 85-87; g) H.-P. van
Schaik, R.-J. Vijn, F. Bickelhaupt, Angew. Chem. Int. Ed. 1994, 33,
1611-1612. Angew. Chem.1994, 106, 1703-1704.
benzocarbocycles • heterocycles• aldehyde–olefin metathesis
[1]
a) K. K.-C. Liu, J. Li, S. Sakya, Mini-Rev. Med. Chem. 2004, 4, 1105-
1125; b) A. Saklani, S. K. Kutty, Drug Discovery Today 2008, 13, 161-
171; c) K. C. Nicolaou, E. J. Sorensen, Classics in Total Synthesis:
Targets, Strategies, Methods, Wiley-VCH, Weinheim, 1996; d) K. C.
Nicolaou, S. A. Snyder, Classics in Total Synthesis II: More Targets,
Strategies, Methods, Wiley-VCH, Weinheim, 2003; e) M. Gehringer, S.
A. Laufer, J. Med. Chem. 2018, 10.1021/acs.jmedchem.8b01153; f) X.
Zhang, K.P. Rakesh, S. N. A. Bukhari, M. Balakrishna. H. L. Qin, Bioorg.
Chem. 2018, 80, 86-93; g) H. M. Revankar, S. N. A. Bukhari, G. B.
Kumar, H. L. Qin, Bioorg. Chem. 2017, 71, 146-159.
[11] a) L. Catti, K. Tiefenbacher, Angew. Chem. Int. Ed. 2018, 57, 14589-
14592; Angew. Chem. 2018, 130, 14797-14800; b) U. P. N. Tran, G.
Oss, M. Breugst, E. Detmar, D. P. Pace, K. Liyanto, T. V. Nguyen, ACS
Catalysis, 2019, 9, 912-919.
[12] a) H. Albright, H. L.Vonesh, M. R. Becker, B. W. Alexander, J. R.
Ludwig, R. A. Wiscons, C. S. Schindler, Org. Lett. 2018, 20, 4954-4958;
b) L. Pitzer, F. Sandfort, F. Strieth-Kalthoff, F. Glorius, Angew. Chem.
Int. Ed. 2018, 57, 16219-16223; Angew. Chem. 2018, 130, 16453-
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