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Synlett 2023; 34(12): 1442-1446
DOI: 10.1055/a-2021-9514
cluster
Special Issue Honoring Masahiro Murakami’s Contributions to Science

Enantioselective Synthesis of Axially Chiral 1-Arylisoquinolines by Iridium(I)-Catalyzed Hydroarylation of Alkynes

Qiansujia Zhou
a   College of Science, University of Shanghai for Science and Technology, Shanghai 200093, P. R. of China
b   State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
,
Si-Yong Yin
b   State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
,
Dong-Song Zheng
b   State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
,
Wen-Wen Zhang
b   State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
,
Su-Zhen Zhang
a   College of Science, University of Shanghai for Science and Technology, Shanghai 200093, P. R. of China
b   State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
,
Qing Gu∗
a   College of Science, University of Shanghai for Science and Technology, Shanghai 200093, P. R. of China
b   State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
,
Shu-Li You∗
b   State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
› Author AffiliationsWe thank National Key R&D Program of China (2021YFA1500100), NSFC (21821002, 92256302, and 22071260), Science and Technology Commission of Shanghai Municipality (21520780100) for generous financial support.
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Abstract

Ir(I)-catalyzed atroposelective hydroarylation of alkynes with 1-arylisoquinolines through C–H functionalization was realized. In the presence of 5 mol% of [Ir(cod)Cl]2 and 10 mol% of QUINOX-P, a wide range of axially chiral alkenylated biaryls were obtained in up to 98% yield and 97% ee. Notably, only one equivalent of the alkyne was required to guarantee a high efficiency of this C–H functionalization process. This reaction exhibits excellent functional-group tolerance under mild conditions.

Key words

alkynes - isoquinolines - axial chirality - C–H functionalization - iridium catalysis - asymmetric synthesis

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2021-9514.
  • Supporting Information


Publication History

Received: 10 January 2023

Accepted after revision: 29 January 2023

Accepted Manuscript online:
29 January 2023

Article published online:
22 February 2023

© 2023. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

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  • 14 (S a,E)-1-[2-(1,2-Bis(4-methoxyphenyl)vinyl]-1-naphthyl)benzo[h]isoquinoline (3aa) Yellow foam; yield: 105.7 mg (97%, 96% ee); [α]D 24 –394.9 (c = 0.2, CHCl3). HPLC [Chiralpak AD-H column (4.6 × 250 mm), hexane/i-PrOH (90:10); flow rate: 1.0 mL/min, λ = 254 nm, 25 ℃]. t R (minor) = 8.23 min; t R (major) = 23.86 min. IR (ATR): = 2925, 2854, 1605, 1509, 1462, 1291, 1247, 1176, 1033, 853, 826, 752, 669 cm–1. 1H NMR (400 MHz, CDCl3): δ = 8.57 (d, J = 5.2 Hz, 1 H), 8.01 (d, J = 8.4 Hz, 1 H), 7.95 (d, J = 8.0 Hz, 1 H), 7.83–7.75 (m, 2 H), 7.62 (d, J = 8.4 Hz, 1 H), 7.57 (d, J = 8.8 Hz, 1 H), 7.52–7.46 (m, 2 H), 7.46–7.41 (m, 2 H), 7.38 (d, J = 8.4 Hz, 1 H), 7.28–7.19 (m, 1 H), 7.08–7.00 (m, 1 H), 6.48–6.48 (m, 4 H), 6.27 (d, J = 8.4 Hz, 2 H), 6.16 (s, 1 H), 6.09 (d, J = 8.4 Hz, 2 H), 3.62 (s, 3 H), 3.52 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 158.0, 157.7, 157.1, 143.6, 140.7, 140.2, 139.1, 137.8, 133.5, 133.1, 132.2, 132.1, 131.9, 130.9, 130.6, 130.22, 130.17, 129.6, 129.3, 128.7, 128.4, 128.1, 126.92, 126.90, 126.86, 126.6, 126.4, 126.3, 126.0, 125.5, 120.9, 113.1, 112.8, 55.1, 55.0. HRMS (ESI-TOF): m/z [M + H]+ calcd for C39H30NO2: 544.2271; found: 544.2265.
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  • 17 1-(2-[1,2-Diarylvinyl]-1-naphthyl)benzo[h]isoquinolines 3: General Procedure Under an argon atmosphere, a flame-dried 10 mL Schlenk tube was charged with [Ir(cod)Cl]2 (6.7 mg, 0.01 mmol, 5 mol%), (S,S)-QUINOX-P (6.6 mg, 0.02 mmol, 10 mol%) and anhyd THF (1.0 mL), and the resulting solution was stirred for 10 min at rt. Then, isoquinoline 1 (0.2 mmol), alkyne 2 (0.2 mmol), and NaBArF (35.4 mg, 0.04 mmol, 20 mol%) were added under argon and the tube was heated at 80 °C for 10–24 h. The mixture was then cooled to rt and the crude product was purified by preparative TLC (PE–EtOAc, 5:1).