Catalytic C2 prenylation of unprotected indoles: Late-stage diversification of peptides and two-step total synthesis of tryprostatin B

doi:10.1016/S1872-2067(20)63780-9

Chinese Journal of Catalysis ›› 2021, Vol. 42 ›› Issue (9): 1593-1607.DOI: 10.1016/S1872-2067(20)63780-9

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Catalytic C2 prenylation of unprotected indoles: Late-stage diversification of peptides and two-step total synthesis of tryprostatin B

Yan-Cheng Hu^a^,^b^,^†, Ying Li^a^,^b^,^†, Ding-Wei Ji^a^,^b, Heng Liu^a^,^b, Hao Zheng^a^,^b, Gong Zhang^a^,^b, Qing-An Chen^a^,^b^,^*()

^aDalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2021-01-02 Accepted:2021-02-07 Online:2021-09-18 Published:2021-05-16
Contact: Qing-An Chen
About author:^* Tel: +86-411-84379260; Fax: +86-411-84379223; E-mail: qachen@dicp.ac.cn
Qing-An Chen (Dalian Institute of Chemical Physics, Chinese Academy of Sciences) was born in 1984 in Fujian Province, China. He received a B.S. degree from University of Science and Technology of China in 2007 and earned his Ph.D. from Dalian Institute of Chemical Physics under the supervision of Prof. Yong-Gui Zhou in 2012. He worked with Prof. Vy M. Dong at the University of California Irvine as a postdoctoral fellow from 2012 to 2015. Then he joined Prof. Martin Oestreich's group at Technische Universitat Berlin as an Alexander von Humboldt Fellow. In 2017 he began his independent research career at the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, where currently he is Professor of Chemistry. His research interests include the development of catalytic alkene functionalization, asymmetric synthesis and biomimetic catalysis. He has authored over 44 publications and 20 patents. In 2020, he received Thieme Chemistry Journal Award and was appointed as a young member of Editorial Board (2020-2024) of Chinese Journal of Catalysis.First author contact:
^† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21801239);National Natural Science Foundation of China(22071239)

Abstract

Abstract:

C2 prenylated indoles are widespread in a variety of bioactive natural alkaloids. Therefore, the selective installation of prenyl group at C2 position of NH indoles is of great significance. However, the known protocols generally require a multi-step procedure and stoichiometric promoters. Herein we develop a one-step C2 prenylation of NH indole with cheap tert-prenyl alcohol enabled by acid catalysis. Salient features include good regioselectivity, step- and atom-economy, broad substrate scope, and simple catalytic system. The mechanistic investigations demonstrate that both C2 prenylation and C3 prenylation/migration pathways are engaged in the reaction. Notably, this practical strategy can be applied to the late-stage diversification of tryptophan-based peptides and concise synthesis of tryprostatin B.

Key words: Indole prenylation, Step economy, Atom economy, Tryptophan, Peptide diversification, Total synthesis

Yan-Cheng Hu, Ying Li, Ding-Wei Ji, Heng Liu, Hao Zheng, Gong Zhang, Qing-An Chen. Catalytic C2 prenylation of unprotected indoles: Late-stage diversification of peptides and two-step total synthesis of tryprostatin B[J]. Chinese Journal of Catalysis, 2021, 42(9): 1593-1607.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63780-9

https://www.cjcatal.com/EN/Y2021/V42/I9/1593

Figures/Tables 8

Fig. 1. Representative C2 prenylated indole alkaloids.

Fig. 2. An overview on C2 prenylation of NH indoles.

Table 1 Optimization of C2 prenylation of tryptophol. a


Entry	Acid	Solvent	T (°C)	Yield ^b (%)	3a:3a’ ^c
1	CSA	DCE	70	39	3:1
2	Tf₂NH	DCE	70	22	4:1
3	AlCl₃	DCE	70	46	5:1
4	FeCl₃	DCE	70	29	10:1
5	Bi(OTf)₃	DCE	70	Mixture	—
6	Sc(OTf)₃	DCE	70	Mixture	—
7	BF₃·Et₂O	DCE	70	Mixture	—
8	Amberlyst-15 ^d	DCE	70	57	4:1
9	Nafion ^e	DCE	70	54	3:1
10	AlCl₃	PhCl	70	56	10:1
11	AlCl₃	NMP	70	N.R.	—
12	AlCl₃	dioxane	70	69	12:1
13	AlCl₃	THF	70	66	10:1
14	AlCl₃	2-MeTHF	70	67	12:1
15	AlCl₃	2-MeTHF	80	75	12:1
16	Al(OTf)₃	2-MeTHF	80	Mixture	—
17	AlMe₃	2-MeTHF	80	N.R.	—
18	Cu(OTf)₂	2-MeTHF	80	N.R.	—
19	Zn(OTf)₂	2-MeTHF	80	19	5:1
20	Mg(ClO₄)₂	2-MeTHF	80	N.R.	—
21	Al(OⁱPr)₃	2-MeTHF	80	N.R.	—
22	Al(OⁱPr)₃/HCl ^f	2-MeTHF	80	46	6:1

Fig. 3. Catalytic C2 prenylation of 3-substituted indoles. Reaction conditions: 1 (0.40 mmol), 2 (1.20 mmol), AlCl3 (10 mol%-30 mol%), 2-MeTHF or PhCl (0.40 mL), 80 °C, 24 h. Isolated yields were given. The ratio (3/3’) was determined by 1H NMR, unless otherwise stated, the ratio was > 20:1. a AlCl3 (30 mol%). b Amberlyst-15 (12.0 mg), 100 °C for 24 h. c Nafion (9.4 mg).

Fig. 4. Late-stage prenylation of tryptophanate and peptide. Reaction conditions: 4 (0.40 mmol), 2 (1.20 mmol), AlCl3 (30 mol%), PhCl (0.40 mL), 80 °C, 24 h. Isolated yields were given. The ratio (5/5’) was determined by 1H NMR, unless otherwise stated, the ratio was > 20:1.

Fig. 5. Concise synthesis of tryprostatin B and cyclodipeptide.

Fig. 6. Mechanistic investigation.

Fig. 7. Isomerization of prenyl group. Reaction conditions for one-step procedure: 1 (0.40 mmol), 2 (2.40 mmol), Nafion (9.4 mg), [Bmim]Cl (0.50 g), 120 °C, 24 h. [Bmim]Cl = 1-Butyl-3-methylimidazolium chloride.

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Catalytic C2 prenylation of unprotected indoles: Late-stage diversification of peptides and two-step total synthesis of tryprostatin B

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