Asymmetric Dearomatization of Indole Derivatives with N-Hydroxycarbamates Enabled by Photoredox Catalysis

doi:10.1002/anie.201911144

Review

. 2019 Dec 9;58(50):18069-18074.

doi: 10.1002/anie.201911144. Epub 2019 Oct 24.

Asymmetric Dearomatization of Indole Derivatives with N-Hydroxycarbamates Enabled by Photoredox Catalysis

Yuan-Zheng Cheng¹, Qing-Ru Zhao^{1

2}, Xiao Zhang¹, Shu-Li You^{1

2}

Affiliations

¹ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China.
² School of Physical Science and Technology, ShanghaiTech University, 100 Haike Road, Shanghai, 201210, China.

PMID: 31587423
DOI: 10.1002/anie.201911144

Review

Asymmetric Dearomatization of Indole Derivatives with N-Hydroxycarbamates Enabled by Photoredox Catalysis

Yuan-Zheng Cheng et al. Angew Chem Int Ed Engl. 2019.

. 2019 Dec 9;58(50):18069-18074.

doi: 10.1002/anie.201911144. Epub 2019 Oct 24.

Authors

Yuan-Zheng Cheng¹, Qing-Ru Zhao^{1

2}, Xiao Zhang¹, Shu-Li You^{1

2}

Affiliations

¹ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China.
² School of Physical Science and Technology, ShanghaiTech University, 100 Haike Road, Shanghai, 201210, China.

PMID: 31587423
DOI: 10.1002/anie.201911144

Abstract

Dearomatization of indoles provides efficient synthetic routes for substituted indolines. In most cases, indoles serve as nucleophiles. Reported here is an asymmetric dearomatization reaction of indole derivatives that function as electrophiles. The combination of a photocatalyst and chiral phosphoric acid open to air unlocks the umpolung reactivity of indoles, enabling their dearomatization with N-hydroxycarbamates as nucleophiles. A variety of fused indolines bearing intriguing oxy-amines were constructed in excellent yields with moderate to high enantioselectivities. Mechanistic studies show that the realization of two sequential single-electron transfer oxidations of the indole derivatives is key, generating the configurationally biased carbocation species while providing the source of stereochemical induction. These results not only provide an efficient synthesis of enantioenriched indoline derivatives, but also offer a novel strategy for further designing asymmetric dearomatization reactions.

Keywords: asymmetric synthesis; dearomatization; indoles; photochemistry; umpolung.

PubMed Disclaimer

Cited by

Diastereoselective dearomatization of indoles via photocatalytic hydroboration on hydramine-functionalized carbon nitride.
Zhang Q, Xu W, Liu Q, Xia C, Shao Q, Ma L, Wu M. Zhang Q, et al. Nat Commun. 2024 May 22;15(1):4371. doi: 10.1038/s41467-024-48769-1. Nat Commun. 2024. PMID: 38778032 Free PMC article.
Tunable C-H functionalization and dearomatization enabled by an organic photocatalyst.
An B, Cui H, Zheng C, Chen JL, Lan F, You SL, Zhang X. An B, et al. Chem Sci. 2024 Feb 6;15(11):4114-4120. doi: 10.1039/d4sc00120f. eCollection 2024 Mar 13. Chem Sci. 2024. PMID: 38487217 Free PMC article.
Diversity-Oriented Catalytic Asymmetric Dearomatization of Indoles with o-Quinone Diimides.
Gao HJ, Miao YH, Sun WN, Zhao R, Xiao X, Hua YZ, Jia SK, Wang MC, Mei GJ. Gao HJ, et al. Adv Sci (Weinh). 2023 Dec;10(35):e2305101. doi: 10.1002/advs.202305101. Epub 2023 Oct 23. Adv Sci (Weinh). 2023. PMID: 37870177 Free PMC article.
Mechanistic duality of indolyl 1,3-heteroatom transposition.
Lee Y, Nam YS, Kim SY, Ki JE, Lee HG. Lee Y, et al. Chem Sci. 2023 Jun 16;14(28):7688-7698. doi: 10.1039/d3sc00716b. eCollection 2023 Jul 19. Chem Sci. 2023. PMID: 37476715 Free PMC article.
Organophotocatalytic dearomatization of indoles, pyrroles and benzo(thio)furans via a Giese-type transformation.
Zhang Y, Ji P, Gao F, Dong Y, Huang H, Wang C, Zhou Z, Wang W. Zhang Y, et al. Commun Chem. 2021 Feb 19;4(1):20. doi: 10.1038/s42004-021-00460-y. Commun Chem. 2021. PMID: 36697532 Free PMC article.

See all "Cited by" articles

References

1. For selected reviews, see:
1. M. Somei, F. Yamada, Nat. Prod. Rep. 2005, 22, 73;
1. G. R. Humphrey, J. T. Kuethe, Chem. Rev. 2006, 106, 2875;
1. M. Bandini, A. Eichholzer, Angew. Chem. Int. Ed. 2009, 48, 9608;
1. Angew. Chem. 2009, 121, 9786;

Publication types

Actions
Actions

Grants and funding

LinkOut - more resources

Full Text Sources
- Wiley

[1] For selected reviews, see:

[2] For selected reviews, see:

[3] M. Somei, F. Yamada, Nat. Prod. Rep. 2005, 22, 73;

[4] M. Somei, F. Yamada, Nat. Prod. Rep. 2005, 22, 73;

[5] G. R. Humphrey, J. T. Kuethe, Chem. Rev. 2006, 106, 2875;

[6] G. R. Humphrey, J. T. Kuethe, Chem. Rev. 2006, 106, 2875;

[7] M. Bandini, A. Eichholzer, Angew. Chem. Int. Ed. 2009, 48, 9608;

[8] M. Bandini, A. Eichholzer, Angew. Chem. Int. Ed. 2009, 48, 9608;

[9] Angew. Chem. 2009, 121, 9786;

[10] Angew. Chem. 2009, 121, 9786;

Save citation to file

Email citation

Add to Collections

Add to My Bibliography

Your saved search

Create a file for external citation management software

Your RSS Feed

Asymmetric Dearomatization of Indole Derivatives with N-Hydroxycarbamates Enabled by Photoredox Catalysis

Affiliations

Asymmetric Dearomatization of Indole Derivatives with N-Hydroxycarbamates Enabled by Photoredox Catalysis

Authors

Affiliations

Abstract

Similar articles

Cited by

References

Publication types

Grants and funding

LinkOut - more resources

Full Text Sources