10.1002/anie.202107856
Angewandte Chemie International Edition
COMMUNICATION
Weinheim: Germany, 2010; Chapter 10, pp 799-838; b) C. Godard, B.
K. Muñoz, A. Ruiz, C. Claver, Dalton Trans. 2008, 853-860.
a) C. H. Low, J. D. Nobbs, M. van Meurs, L. P. Stubbs, E. Drent, S.
Aitipamula, M. H. L. Pung, Organometallics 2015, 34, 4281-4292; b) A.
Aghmiz, M. Giménez-Pedrós, A. M. Masdeu-Bultó, F. P. Schmidtchen,
Catal. Lett. 2005, 103, 191-193.
arenes with CO and water. The straightforward, mild and
operationally simple protocol has enabled facile assembly of a
range of 2-arylpropanoic acids in high yields and
enantioselectivities. Several non-steroidal anti-inflammatory
drugs including ibuprofen, naproxen, flurbiprofen, fenoprofen,
and ketoprofen were synthesized in gram scale through the
protocol. The catalytic system has also enabled an asymmetric
Markovnikov hydroalkoxycarbonylation of vinyl arenes with
alcohols for the synthesis of 2-arylpropanates. Mechanistic
investigations revealed that the reactions proceed through a
palladium-hydride pathway, the hydropalladation is irreversible
and is the regio- and enantiodetermining step, while
hydrolysis/alcoholysis is probably the rate-limiting step. Further
scope and mechanistic studies of such reactions are underway
in our laboratory.
[6]
[7]
[8]
[9]
a) V. Goldbach, L. Falivene, L. Caporaso, L. Cavallo, S. Mecking, ACS
Catal. 2016, 6, 8229-8238; b) A. Ionescu, G. Laurenczy, O. F. Wendt,
Dalton Trans., 2006, 3934-3940.
a) B. Jiang, Z.-G. Huang, K.-J. Cheng, Heterocycles 2004, 63, 2797-
2803; b) C. Botteghi, G. Consiglio; P. Pino, Chimia 1973, 27, 477-478;
c) G. Consiglio, J. Organomet. Chem. 1977, 132, C26-C27.
M. D. Miquel-Serrano, A. Aghmiz, M. Diéguez, A. M. Masdeu-Bultó, C.
Claver, D. Sinou, Tetrahedron: Asymmetry 1999, 10, 4463-4467.
[10] a) I. del Río, N. Ruiz, C. Claver, Inorg. Chem. Commun. 2000, 3, 166-
168; b) N. Ruiz, I. del Río, J. L. Jiméne, C. Claver, J. Forniés-Cámer, C.
C.J. Cardin, S. Gladiali,J. Mol. Catal. A: Chem. 1999, 143, 171-180; c)
K. Nozaki, M. L. Kantam, T. Horiuchi, H. Takaya, J. Mol. Catal. A:
Chem. 1997, 118, 247-253.
[11] a) B. K. Muñoz, C. Godard, A. Marinetti, A. Ruiz, J. Benet-Buchholz, C.
Claver, Dalton Trans. 2007, 5524-5530; b) B. Muñoz, A. Marinetti, A.
Ruiz, S. Castillon, C. Claver, Inorg. Chem. Commun. 2005, 8, 1113-
1115; c) Y. Kawashima, K. Okano, K. Nozaki, T. Hiyama, Bull. Chem.
Soc. Jpn. 2004, 77, 347-355; d) K. Nozaki, M. L. Kantam, T. Horiuchi, H.
Takaya, J. Mol. Catal. A 1997, 118, 247-253.
Acknowledgements
This work was supported by generous grants from the National
Natural Science Foundation of China (NSFC-21971204,
21622203), the Innovation Capability Support Program of
Shaanxi Province (No. 2020TD-022) and Fund of Education
Department of Shaanxi Provincial Government (21JP121).
[12] T. M. Konrad, J. A. Fuentes, A. M. Z. Slawin, M. L. Clarke, Angew.
Chem. 2010, 122, 9383-9386; Angew. Chem. Int. Ed. 2010, 49, 9197-
9200.
[13] a) G. J. Harkness, M. L. Clarke, Eur. J. Org. Chem. 2017, 2017, 4859-
4863; b) T. M. Konrad, J. T. Durrani, C. J. Cobley, M. L. Clarke, Chem.
Commun. 2013, 49, 3306-3308.
Keywords: synthetic methods • carbon monoxide •
enantioselectivity • vinyl arenes • 2-arylpropanoic acids
[14] Z. Huang, Y. Cheng, X. Chen, H.-F. Wang, C.-X. Du, Y. Li, Chem.
Commun. 2018, 54, 3967-3970.
[1]
For reviews, see: a) B. E. Ali, H. Alper in Transition Metals for Organic
Synthesis, 2nd ed. (Eds.: M. Beller, C. Bolm), Wiley-VCH, Weinheim,
2004, pp. 113-132; b) S. Zhang, H. Neumann, M. Beller, Chem. Soc.
Rev. 2020, 49, 3187-3210; c) A. ennf h e , H. Neumann, M. Beller,
ChemCatChem 2009, 1, 28-41; d) R. Franke, D. Selent, A. ne ,
Chem. Rev. 2012, 112, 5675-5732; e) G. Kiss, Chem. Rev. 2001, 101,
3435-3456.
[15] a) M. Chen, X. Wang, P. Yang, X. Kou, Z.-H. Ren, Z.-H. Guan, Angew.
Chem. 2020, 132, 12297-12303; Angew. Chem. Int. Ed. 2020, 59,
12199-12205; b) Y.-H. Yao, H.-Y. Yang, M. Chen, F. Wu, X.-X. Xu, Z.-H.
Guan, J. Am. Chem. Soc. 2021, 143, 85-91.
[16] a) F. Bertoux, E. Monflier, Y. Castanet, A. Mortreux, J. Mol. Catal. A:
Chem. 1999, 143, 23-30; b) M. Karlsson, A. Ionescu, C. Andersson, J.
Mol. Catal. A: Chem. 2006, 259, 231-237.
[2]
For examples, see: a) D. M. Hood, R. A. Johnson, A. E. Carpenter, J. M.
Younker, D. J. Vinyard, G. G. Stanley, Science 2020, 367, 542-548; b)
Y. Yuan, F.-P. Wu, C. Schünemann, J. Holz, P. C. J. Kamer, X.-F. Wu,
Angew. Chem. 2020, 132, 22627-22631; Angew. Chem. Int. Ed. 2020,
59, 22441-22445; c) J. Yang, J. Liu, H. Neumann, R. Frank, R.
Jackstell, M. Beller, Science 2019, 366, 1514-1517; d) X. Wang, B.
Wang, X. Yin, W. Yu, Y. Liao, J. Ye, M. Wang, L. Hu, J. Liao, Angew.
Chem. 2019, 131, 12392-12398; Angew. Chem. Int. Ed. 2019, 58,
12264-12270.
[17] a) H.-Y. Yang, Y.-H. Yao, M. Chen, Z.-H. Ren, Z.-H. Guan, J. Am.
Chem. Soc. 2021, 143, 7298-7305; b) M. De La Higuera Macias, B. A.
Arndtsen, J. Am. Chem. Soc. 2018, 140, 10140-10144; c) J. S. Quesnel,
B. A. Arndtsen, J. Am. Chem. Soc. 2013, 135, 16841-16844; d) E. J.
Jang, K. H. Lee, J. S. Lee, Y. G. Kim, J. Mol. Catal. A: Chem. 1999,
138, 25-36.
[18] a) A. Glis c ńs a, E. Sánche -López, Pharmaceutics 2021, 13, 414-
432; b) B. Kasprzyk-Hordern, Chem. Soc. Rev. 2010, 39, 4466-4503; c)
Nonsteroidal Anti Inflammatory Drugs: Mechanisms and Clinical Uses;
(Eds.: A. J. Lewis, D. E. Furst), Marcel Dekker: New York, 1994.
[19] a) M. L. Abrams, J. Y. Buser, J. R. Calvin, M. D. Johnson, B. R. Jones,
G. Lambertus, C. R. Landis, J. R. Martinelli, S. A. May, A. D. McFarland,
J. R. Stout, Org. Process Res. Dev. 2016, 20, 901-910; b) P. J.
Harrington, E. Lodewijk, Org. Process Res. Dev. 1997, 1, 72-76; c) T.
Wu, B. Rouge, Patent US 5902898, 1999; d) R. Hardy, P. F. Coe, A.
Hirst, H. O. O’ onnell, Patent US 5599969, 1997.
[3]
[4]
a) Bioactive Carboxylic Compound Classes: Pharmaceuticals and
Agrochemicals. (Eds.: C. Lamberth, J. Dinges) Wiley-VCH: 2016; b) P.
Bhutani, G. Joshi, N. Raja, N. Bachhav, P. K. Rajanna, H. Bhutani, A. T.
Paul, R. U.S. Kumar, J. Med. Chem. 2021, 64, 2339-2381; c) A.
Varenikov, E. Shapiro, M. Gandelman, Chem. Rev. 2021, 121, 412-
484; d) F. Stempfle, P. Ortmann, S. Mecking, Chem. Rev. 2016, 116,
4597-4641.
For examples, see: a) R. Sang, P. uc ie c , R. h en, R. Ra a ,
K. Dong, J. Liu, R. Franke, R. Jackstell, M. Beller, Angew. Chem. 2019,
131, 14503-14511; Angew. Chem. Int. Ed. 2019, 58, 14365-14373; b)
W. Ren, J. Chu, F. Sun, Y. Shi, Org. Lett. 2019, 21, 5967-5970; c) W.
Liu, W. Ren, J. Li, Y. Shi, W. Chang, Y. Shi, Org. Lett. 2017, 19, 1748-
1751; d) J. J. R. Frew, K. Damian, H. V. Rensburg, A. M. Z. Slawin, R.
P. Tooze, M. L. Clarke, Chem. Eur. J. 2009, 15, 10504-10513; e) A.
Seayad, S. Jayasree, R. V. Chaudhari, Org. Lett. 1999, 1, 459-461; f)
W. Reppe, Justus Liebigs Ann. Chem. 1953, 582, 1-37; g) W. F.
Gresham, R. E. Brooks, Patent US 2448368, 1948.
[20] For examples, see: a) K. Dong, X. Fang, S. Gülak, R. Franke, A.
Spannenberg, H. Neumann, R. Jackstell, M. Beller, Nat. Commun.
2017, 8, 14117; b) H. Li, K. Dong, H. Jiao, H. Neumann, R. Jackstell, M.
Beller, Nat. Chem. 2016, 8, 1159-1166; c) . A uita-Valencia, H.
Alper, J. Org. Chem. 2016, 81, 3860-3867.
[21] For examples, see: a) J. Li, W. Chang, W. Ren, J. Dai, Y. Shi, Org. Lett.
2016, 18, 5456-5459; b) C. Godard, A. Ruiz, C. Claver, Helv. Chim.
Acta 2006, 89, 1610-1655; c) D. Tian, R. Xu, J. Zhu, J. Huang, W.
Dong, J. Claverie, W. Tang, Angew. Chem. 2021, 133, 6375-6379;
Angew. Chem. Int. Ed. 2021, 60, 6305-6309; d) X. Ren, Z. Wang, C.
Shen, X. Tian, L. Tang, X. Ji, K. Dong, Angew. Chem. Int. Ed. 2021, 60,
doi: 10.1002/anie.202105977; e) J. Li, W. Chang, W. Ren, W. Liu, H.
Wang, Y. Shi, Org. Biomol. Chem. 2015, 13, 10341-10347; f) P. Cao, X.
[5]
a) C. Godard, A. Ruiz, M. Diéguez, O. Pàmies, C. Claver in Catalytic
Asymmetric Synthesis; 3rd ed. (Ed.: I. Ojima) John Wiley & Sons:
5
This article is protected by copyright. All rights reserved.