When is an Imine Directing Group a Transient Imine Directing Group in C-H Functionalization?

Publisher: Wiley-VCH Country of Publication: Germany NLM ID: 9513783 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1521-3765 (Electronic) Linking ISSN: 09476539 NLM ISO Abbreviation: Chemistry Subsets: PubMed not MEDLINE; MEDLINE

Original Publication: Weinheim, Germany : Wiley-VCH

'Transient' C-H functionalization has emerged in recent years to describe the use of a dynamic linkage, often an imine, to direct cyclometallation and subsequent functionalization. As the field continues to grow in popularity, we consider the features that make an imine directing group transient. A transient imine should be i) formed dynamically in situ, ii) avoid discrete introduction or cleavage steps, and iii) offer the potential for catalysis in both the directing group and metal. This concept article contrasts transient imines with pioneering early studies of imines as directing groups for the formation of metallacycles and the use of preformed imines in C-H functionalization. Leading developments in the use of catalytic additives to form transient directing groups (as aldehyde or amine) are covered including selected highlights of the most recent examples of catalytic imine directed C-H functionalization with transition metals.
(© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

For early work exploring C−H metalation, see:.
J. P. Kleiman, M. Dubeck, J. Am. Chem. Soc. 1963, 85, 1544–1545;.
M. M. Bagga, W. T. Flannigan, G. R. Knox, P. L. Pauson, F. J. Preston, R. I. Reed, J. Chem. Soc. C Org. 1968, 36–40;.
A. C. Cope, E. C. Friedrich, J. Am. Chem. Soc. 1968, 90, 909–913;.
C. B. Knobler, S. S. Crawford, H. D. Kaesz, Inorg. Chem. 1975, 14, 2062–2066;.
S. Komiya, A. Yamamoto, Chem. Lett. 1975, 4, 475–478;.
R. J. Foot, B. T. Heaton, J. Chem. Soc. Dalt. Trans. 1979, 15, 295;.
M. F. McGuiggan, L. H. Pignolet, Inorg. Chem. 1982, 21, 2523–2526;.
G. Balavoine, J. C. Client, J. Organomet. Chem. 1990, 390, 84–88.
For general reviews on C−H activation, see:.
J. Wencel-Delord, T. Dröge, F. Liu, F. Glorius, Chem. Soc. Rev. 2011, 40, 4740–4761;.
J. Yamaguchi, A. D. Yamaguchi, K. Itami, Angew. Chem. Int. Ed. 2012, 51, 8960–9009;.
J. He, M. Wasa, K. S. L. Chan, Q. Shao, J.-Q. Yu, Chem. Rev. 2017, 117, 8754–8786;.
N. Y. S. Lam, K. Wu, J.-Q. Yu, Angew. Chem. Int. Ed. 2021, 60, 15767–15790.
For reviews of transient C−H functionalization, see:.
P. Gandeepan, L. Ackermann, Chem 2018, 4, 199–222;.
S. St John-Campbell, J. A. Bull, Org. Biomol. Chem. 2018, 16, 4582–4595;.
B. Niu, K. Yang, B. Lawrence, H. Ge, ChemSusChem 2019, 12, 2955–2969;.
J. I. Higham, J. A. Bull, Org. Biomol. Chem. 2020, 18, 7291–7315;.
N. Goswami, T. Bhattacharya, D. Maiti, Nat. Chem. Rev. 2021, 5, 646–659;.
B. Zu, Y. Guo, J. Ke, C. He, Synthesis 2021, 53, 2029–2042;.
C. Jacob, B. U. W. Maes, G. Evano, Chem. - Eur. J. 2021, 27, 13899–13952;.
J. Das, W. Ali, D. Maiti, Trends Chem. 2023, 5, 551–560;.
H. Amistadi-Revol, S. Liu, S. Prévost, Eur. J. Org. Chem. 2023, 26, e202300582.
S. Murahashi, J. Am. Chem. Soc. 1955, 77, 6403–6404.
 .
P. W. Clark, S. F. Dyke, G. Smith, C. H. L. Kennard, J. Organomet. Chem. 1987, 330, 447–460;.
J. Albert, M. Gomez, J. Granell, J. Sales, Organometallics 1990, 9, 1405.
A. G. Constable, W. S. McDonald, L. C. Sawkins, B. L. Shaw, J. Chem. Soc. Chem. Commun. 1978, 1061–1062.
J. A. Johnson, D. Sames, J. Am. Chem. Soc. 2000, 122, 6321–6322.
B. D. Dangel, K. Godula, S. W. Youn, B. Sezen, D. Sames, J. Am. Chem. Soc. 2002, 124, 11856–11857.
 .
S. R. Neufeldt, M. S. Sanford, Org. Lett. 2010, 12, 532–535;.
A. R. Dick, K. L. Hull, M. S. Sanford, J. Am. Chem. Soc. 2004, 126, 2300–2301.
 .
Y. Wang, X. Liu, X. Xu, L. Hao, Y. Ji, Org. Lett. 2023, 25, 4962–4967;.
S. Rej, N. Chatani, J. Am. Chem. Soc. 2021, 143, 2920–2929;.
L. Zhang, J. Gao, B. Wang, A. Iqbal, W. Jin, Y. Xia, Y. Zhang, C. Liu, Org. Chem. Front. 2023, 10, 6063–6069.
Y. Xu, M. C. Young, C. Wang, D. M. Magness, G. Dong, Angew. Chem. Int. Ed. 2016, 55, 9084–9087.
S. Bag, S. Jana, S. Pradhan, S. Bhowmick, N. Goswami, S. K. Sinha, D. Maiti, Nat. Commun. 2021, 12, 1393.
C.-H. Jun, H. Lee, J.-B. Hong, J. Org. Chem. 1997, 62, 1200–1201.
F.-L. Zhang, K. Hong, T.-J. Li, H. Park, J.-Q. Yu, Science 2016, 351, 252–256.
For discussion of the unique properties of HFIP with respect to C−H functionalization, see:.
S. K. Sinha, T. Bhattacharya, D. Maiti, React. Chem. Eng. 2019, 4, 244–253;.
T. Bhattacharya, A. Ghosh, D. Maiti, Chem. Sci. 2021, 12, 3857–3870.
For works applying a transient directing group strategy beyond C−H activation, see:.
L. J. Oxtoby, Z. Li, V. T. Tran, T. G. Erbay, R. Deng, P. Liu, K. M. Engle, Angew. Chem. Int. Ed. 2020, 59, 8885–8890;.
Z. Liu, L. J. Oxtoby, M. Liu, Z. Q. Li, V. T. Tran, Y. Gao, K. M. Engle, J. Am. Chem. Soc. 2021, 143, 8962–8969.
X. H. Liu, H. Park, J. H. Hu, Y. Hu, Q. L. Zhang, B. L. Wang, B. Sun, K. S. Yeung, F. L. Zhang, J.-Q. Yu, J. Am. Chem. Soc. 2017, 139, 888–896.
X. Y. Chen, S. Ozturk, E. J. Sorensen, Org. Lett. 2017, 19, 6280–6283.
X. Y. Chen, E. J. Sorensen, J. Am. Chem. Soc. 2018, 140, 2789–2792.
For leading reports on sp3 C−H functionalization of aldehydes with transient directing groups, see:.
K. Yang, Q. Li, Y. Liu, G. Li, H. Ge, J. Am. Chem. Soc. 2016, 138, 12775–12778;.
S. St John-Campbell, A. J. P. White, J. A. Bull, Chem. Sci. 2017, 8, 4840–4847;.
H. Park, P. Verma, K. Hong, J.-Q. Yu, Nat. Chem. 2018, 10, 755–762;.
S. St John-Campbell, J. A. Bull, Chem. Commun. 2019, 55, 9172–9175;.
S. St John-Campbell, A. J. P. White, J. A. Bull, Org. Lett. 2020, 22, 1807–1812; B.
Li, B. Lawrence, G. Li, H. Ge, Angew. Chem. Int. Ed. 2020, 59, 3078–3082;.
Y.-H. Li, Y. Ouyang, N. Chekshin, J.-Q. Yu, J. Am. Chem. Soc. 2022, 144, 4727–4733.
For advances in transient C−F and C−O bond forming strategies of aldehydes, see:.
H. Park, P. Verma, K. Hong, J.-Q. Yu, Nat. Chem. 2018, 10, 755–762;.
J. Chen, C. Bai, X. Tong, D. Liu, Y.-S. Bao, RSC Adv. 2020, 10, 12192–12196;.
J. Zhou, D. Liu, C. Bai, A. Bao, T. Muschin, M. Baiyin, Y.-S. Bao, Org. Chem. Front. 2021, 8, 5975–5981;.
J. Jiang, D. Yuan, C. Ma, W. Song, Y. Lin, L. Hu, Y. Zhang, Org. Lett. 2021, 23, 279–284;.
S. Liu, S. Prévost, Org. Lett. 2023, 25, 1380–1385;.
M.-S. Mei, Y. Zhang, Org. Lett. 2023, 25, 4985–4989.
 .
B. Chao, C. Bai, H. Yan, R. Zhao, D. Liu, T. Muschin, A. Bao, C. Eerdun, Y.-S. Bao, Org. Lett. 2023, 25, 6823–6829;.
J. Sun, Y. Hu, C.-X. Liao, W.-J. He, Q. Wong, K. Engle, ChemRxiv 2023, DOI 10.26434/chemrxiv-2023-nlvw0.
 .
U. Dhawa, C. Tian, T. Wdowik, J. C. A. Oliveira, J. Hao, L. Ackermann, Angew. Chem. Int. Ed. 2020, 59, 13451–13457;.
U. Dhawa, T. Wdowik, X. Hou, B. Yuan, J. C. A. Oliveira, L. Ackermann, Chem. Sci. 2021, 12, 14182–14188.
Z. Yu, Q. Liu, Q. Li, Z. Huang, Y. Yang, J. You, Angew. Chem. Int. Ed. 2022, 61, e202212079.
S. T. Linde, V. Corti, V. H. Lauridsen, J. N. Lamhauge, K. A. Jørgensen, N. M. Rezayee, Chem. Sci. 2023, 14, 3676–3681.
For representative examples of transient C−H functionalization strategies using metals other than palladium, see: Rhodium.
P. W. Tan, N. A. B. Juwaini, J. Seayad, Org. Lett. 2013, 15, 5166–5169;.
C.-X. Liu, F. Zhao, Q. Gu, S.-L. You, ACS Cent. Sci. 2023, 9, 2036–2043; Ruthenium;.
F. Li, Y. Zhou, H. Yang, D. Liu, B. Sun, F. L. Zhang, Org. Lett. 2018, 20, 146–149; Iridium;.
X.-Y. Chen, E. J. Sorensen, Chem. Sci. 2018, 9, 8951–8956;.
J. Zhou, T. Jiao, Q. Fu, J. Wang, J. Lu, L. Yang, J. Wei, S. Wei, X. Cong, N. Hao, Chem. Commun. 2023, 59, 6355–6358; Cobalt;.
J. Huang, J. Ding, T. M. Ding, S. Zhang, Y. Wang, F. Sha, S. Y. Zhang, X. Y. Wu, Q. Li, Org. Lett. 2019, 21, 7342–7345.
J. I. Higham, J. A. Bull, Angew. Chem. Int. Ed. 2022, 61, e202202933.
Y. H. Li, Y. Ouyang, N. Chekshin, J.-Q. Yu, J. Am. Chem. Soc. 2022, 144, 4727–4733.
Y.-Q. Chen, Z. Wang, Y. Wu, S. R. Wisniewski, J. X. Qiao, W. R. Ewing, M. D. Eastgate, J.-Q. Yu, J. Am. Chem. Soc. 2018, 140, 17884–17894.
K. Yang, Z. Li, C. Liu, Y. Li, Q. Hu, M. Elsaid, B. Li, J. Das, Y. Dang, D. Maiti, H. Ge, Chem. Sci. 2022, 13, 5938–5943.
J. T. Cheng, L. J. Xiao, S. Q. Qian, Z. Zhuang, A. Liu, J.-Q. Yu, Angew. Chem. Int. Ed. 2022, 61, e202117233.
Y. Liu, H. Ge, Nat. Chem. 2017, 9, 26–32.
S. St John-Campbell, A. K. Ou, J. A. Bull, Chem. Eur. J. 2018, 24, 17838–17843.
For recent examples of amine functionalization using an imine directing group additive, see:.
Y. Q. Chen, S. Singh, Y. Wu, Z. Wang, W. Hao, P. Verma, J. X. Qiao, R. B. Sunoj, J.-Q. Yu, J. Am. Chem. Soc. 2020, 142, 9966–9974;.
Y. Q. Chen, Y. Wu, Z. Wang, J. X. Qiao, J.-Q. Yu, ACS Catal. 2020, 10, 5657–5662;.
B. Su, A. Bunescu, Y. Qiu, S. J. Zuend, M. Ernst, J. F. Hartwig, J. Am. Chem. Soc. 2020, 142, 7912–7919;.
G. Kang, L.-J. Xiao, K. D. Hesp, C. W. Huh, Y. Lian, P. Richardson, D. C. Schmitt, K. Hong, J.-Q. Yu, Org. Lett. 2023, DOI: 10.1021/acs.orglett.3c01439.
Y. Wu, Y. Q. Chen, T. Liu, M. D. Eastgate, J.-Q. Yu, J. Am. Chem. Soc. 2016, 138, 14554–14557.
A. Yada, W. Liao, Y. Sato, M. Murakami, Angew. Chem. Int. Ed. 2017, 56, 1073–1076.
J. Ghouilem, S. Bazzi, N. Grimblat, P. Retailleau, V. Gandon, S. Messaoudi, Chem. Commun. 2023, 59, 2497–2500.
J. I. Higham, T.-K. Ma, J. A. Bull, Org. Lett. 2023, 25, 5285–5290.

URF\R\201019 Royal Society; RG150444 Royal Society; RGF\EA\180031 Royal Society; UF140161 Royal Society; RPG-2023-153 Leverhulme Trust

Keywords: Catalysis; C−H functionalization; Imine; Transient Directing Group

Date Created: 20240220 Latest Revision: 20240502

20240502

10.1002/chem.202400345

38375941