Citation: Li Sujia, Lü Jian, Luo Sanzhong. Enantioselective Indium(I)/Chiral Phosphoric Acid-catalyzed[4+2] Cycloaddition of Simple Olefin and β, γ-Unsaturated α-Keto Esters[J]. Acta Chimica Sinica, ;2018, 76(11): 869-873. doi: 10.6023/A18060227 shu

Enantioselective Indium(I)/Chiral Phosphoric Acid-catalyzed[4+2] Cycloaddition of Simple Olefin and β, γ-Unsaturated α-Keto Esters

Key Laboratory of Molecular Recognition and Functions, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190

Corresponding author: Lü Jian, lvjian@iccas.ac.cn Luo Sanzhong, luosz@iccas.ac.cn
Received Date: 8 June 2018
Available Online: 26 November 2018
Fund Project: the National Natural Science Foundation of China 21472193the National Natural Science Foundation of China 21521002the Chinese Academy of Sciences QYZDJ-SSW-SLU023the National Natural Science Foundation of China 21390400Project supported by the National Natural Science Foundation of China (Nos. 21390400, 21521002, 21472193) and the Chinese Academy of Sciences (No. QYZDJ-SSW-SLU023)

Figures(2)

Compared with indium(Ⅲ), indium(I) has both vacant p-orbitals and an electron lone pair, showing distinctive catalytic behaviors. However, chiral indium(I) catalysis has been rarely reported. Previously, we have developed asymmetric binary acid catalysis with indium(Ⅲ) and chiral phosphoric acid for a number of enantioselective transformations. Asymmetric binary-acid catalysis in[4+2] cycloaddition of β, γ-unsaturated α-keto esters with different olefins have been reported by our groups over the past five years. In 2013, we developed exo-selective and enantioselective[4+2] cycloaddition of simple industrial feedstock olefins, such as propene and isobutene, styrene and so on, catalyzed by In(BArF)₃/1a. However, the reaction with electron-rich olefins, such as 4-methoxylstyrene did not work very well by indium(Ⅲ) catalysis due to uncontrolled polymerization side pathway. Very recently, we developed a new binary acid system InCl/1a, which could catalyze enantioselective[4+2] annulation of β, γ-unsaturated α-keto esters with much more electron-rich alkoxyallenes. In this study, we reported that the binary acid InCl and 1a was an effective and exo-selective catalyst for the[4+2] cycloaddition of simple olefins. In the presence of InCl (10 mol%) and chiral phosphoric acid 1a (10 mol%), the reaction occurred smoothly to afford the desired cycloadducts in moderate to good yields (20%~93%), with excellent diastereoselectivity (>95:5, exo/endo) and enantioselectivity (up to 99% ee) under the room temperature in CHCl₃. Different olefins, such as styrenes 2, ring-strained norbornene 5a, norbornadiene 5b, and cyclopentadiene dimer 5c all worked well with excellent stereoselectivity under the optimal reaction conditions. More importantly, when 4-methoxylstyrene is used, the reaction can proceeded smoothly to afford[4+2] adduct 4k in 70% yield and good stereoselectivity (>95:5 dr, and 88% ee). The typical procedure for asymmetric[4+2] cycloaddition is as follows:To a dry reaction tube was added chiral phosphoric acid 1a (0.005 mmol, 5 mol%), InCl (0.005 mmol, 5 mol%), 4 MS (10 mg), 3 (0.1 mmol), then CHCl₃ (0.5 mL) and 2 or 5 (0.5 mmol) was added to the mixture. The mixture was stirred for 24 h at room temperature. The mixture was purified by column chromatography to give the desired cycloaddition products 4 or 6.
- asymmetric catalysis,
- [4+2]cycloaddition,
- binary-acid catalysis,
- InCl,
- chiral phosphoric acid
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