Rh-Catalyzed [3+2] Annulation of Cyclic Ketimines and Alkynyl Chloride: A Strategy for Accessing Unsymmetrically Substituted and Highly Functionalizable Indenes

Overview

Journal Org Lett

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2022 Dec 12

PMID 36503272

Authors

Xu Zhao

Chenrui Fan

Jianbo He

Yunfei Luo

Affiliations

Soon will be listed here.

Abstract

Alkynyl chlorides were found to be extraordinarily novel electrophiles, which could afford a single regioisomer of the [3+2] annulation adducts with cyclic ketimines by rhodium catalysis. The alkenyl chloride moiety in the products provided a valuable functional handle for further diverse transformations. Therefore, this research provided not only a synthetic protocol for accessing unsymmetrically substituted indenyl amines but also a highly divergent solution for decorating the substituting group by postmanipulation of the chloride.

References

Mishra A, Mukherjee U, Sarkar W, Meduri S, Bhowmik A, Deb I . Diastereoselective Spirocyclization of Cyclic N-Sulfonyl Ketimines with Nitroalkenes via Iridium-Catalyzed Redox-Neutral Cascade Reaction. Org Lett. 2019; 21(7):2056-2059. DOI: 10.1021/acs.orglett.9b00295. View

Dong L, Qu C, Huang J, Zhang W, Zhang Q, Deng J . Rhodium-catalyzed spirocyclic sultam synthesis by [3+2] annulation with cyclic N-sulfonyl ketimines and alkynes. Chemistry. 2013; 19(49):16537-40. DOI: 10.1002/chem.201303372. View

Sun Z, Chen S, Zhao P . Tertiary carbinamine synthesis by rhodium-catalyzed [3+2] annulation of N-unsubstituted aromatic ketimines and alkynes. Chemistry. 2010; 16(8):2619-27. DOI: 10.1002/chem.200902814. View

Li S, Wu L, Qin L, Zhu Y, Su F, Xu Y . Iridium(III)-Catalyzed Tandem [3 + 2] Annulation: Synthesis of Spirocyclic Phosphoramide Derivatives. Org Lett. 2016; 18(17):4214-7. DOI: 10.1021/acs.orglett.6b01895. View

Zhang J, Ugrinov A, Zhao P . Ruthenium(II)/N-heterocyclic carbene catalyzed [3+2] carbocyclization with aromatic N-H ketimines and internal alkynes. Angew Chem Int Ed Engl. 2013; 52(26):6681-4. PMC: 4310470. DOI: 10.1002/anie.201209031. View

Reddy Chidipudi S, Burns D, Khan I, Lam H . Enantioselective Synthesis of Spiroindenes by Enol-Directed Rhodium(III)-Catalyzed C-H Functionalization and Spiroannulation. Angew Chem Int Ed Engl. 2015; 54(47):13975-9. PMC: 4648053. DOI: 10.1002/anie.201507029. View

Huang J, Song Q, Zhu Y, Qin L, Qian Z, Dong L . Rhodium(III)-catalyzed three-component reaction of imines, alkynes, and aldehydes through C-H activation. Chemistry. 2014; 20(51):16882-6. DOI: 10.1002/chem.201404576. View

Wei W, Scheremetjew A, Ackermann L . Electrooxidative palladium- and enantioselective rhodium-catalyzed [3 + 2] spiroannulations. Chem Sci. 2022; 13(9):2783-2788. PMC: 8890123. DOI: 10.1039/d1sc07124f. View

Zuo Z, Yang X, Liu J, Nan J, Bai L, Wang Y . Ru(II)-catalyzed oxidative spiroannulation of 2-arylphenols with alkynes via a C-H activation/dearomatization strategy. J Org Chem. 2015; 80(6):3349-56. DOI: 10.1021/acs.joc.5b00316. View

10.

Wang F, Jing J, Zhao Y, Zhu X, Zhang X, Zhao L . Rhodium-Catalyzed C-H Activation-Based Construction of Axially and Centrally Chiral Indenes through Two Discrete Insertions. Angew Chem Int Ed Engl. 2021; 60(30):16628-16633. DOI: 10.1002/anie.202105093. View

11.

Li H, Gontla R, Flegel J, Merten C, Ziegler S, Antonchick A . Enantioselective Formal C(sp )-H Bond Activation in the Synthesis of Bioactive Spiropyrazolone Derivatives. Angew Chem Int Ed Engl. 2018; 58(1):307-311. DOI: 10.1002/anie.201811041. View

12.

Qi X, Li Y, Bai R, Lan Y . Mechanism of Rhodium-Catalyzed C-H Functionalization: Advances in Theoretical Investigation. Acc Chem Res. 2017; 50(11):2799-2808. DOI: 10.1021/acs.accounts.7b00400. View

13.

Tran D, Cramer N . Rhodium-catalyzed dynamic kinetic asymmetric transformations of racemic allenes by the [3+2] annulation of aryl ketimines. Angew Chem Int Ed Engl. 2013; 52(40):10630-4. DOI: 10.1002/anie.201304919. View

14.

Huang J, Qin L, Zhu Y, Song Q, Dong L . Multi-site cyclization via initial C-H activation using a rhodium(III) catalyst: rapid assembly of frameworks containing indoles and indolines. Chem Commun (Camb). 2015; 51(14):2844-7. DOI: 10.1039/c4cc07125e. View

15.

Pham M, Cramer N . Enantioselective Access to Spirocyclic Sultams by Chiral Cp(x) -Rhodium(III)-Catalyzed Annulations. Chemistry. 2016; 22(7):2270-3. DOI: 10.1002/chem.201504998. View

16.

Rago A, Dong G . Synthesis of indoles, indolines, and carbazoles palladium-catalyzed C─H activation. Green Synth Catal. 2022; 2(2):216-227. PMC: 9581343. DOI: 10.1016/j.gresc.2021.02.001. View

17.

Zhang Y, Huang T, Li X, Zhang M, Song Y, Huang K . Rh(iii)-catalyzed spiroannulation of 3-arylquinoxalin-2(1)-ones with alkynes: practical access to spiroquinoxalinones. RSC Adv. 2022; 10(37):22216-22221. PMC: 9054490. DOI: 10.1039/d0ra03348k. View

18.

Zheng J, Wang S, Zheng C, You S . Asymmetric Synthesis of Spiropyrazolones by Rhodium-Catalyzed C(sp )-H Functionalization/Annulation Reactions. Angew Chem Int Ed Engl. 2017; 56(16):4540-4544. DOI: 10.1002/anie.201700021. View

19.

Luo Y, Liu H, Zhang J, Liu M, Dong L . Rh(III)-Catalyzed [3 + 2] Spirocyclization of 2-Imidazoles with 1,3-Diynes for the Synthesis of Spiro-[imidazole-indene] Derivatives. Org Lett. 2020; 22(19):7604-7608. DOI: 10.1021/acs.orglett.0c02805. View

20.

Sharma S, Oh Y, Mishra N, De U, Jo H, Sachan R . Rhodium-Catalyzed [3 + 2] Annulation of Cyclic N-Acyl Ketimines with Activated Olefins: Anticancer Activity of Spiroisoindolinones. J Org Chem. 2017; 82(7):3359-3367. DOI: 10.1021/acs.joc.6b02708. View