Efficient Synthesis of Isoquinolines via Rh(III)-Catalyzed Oxidative Annu­lation of Picolinamides with Alkynes

Zhen-Chao Qian; Jun Zhou; Bo Li; Bing-Feng Shi

doi:10.1055/s-0033-1340870

Synlett, Inhaltsverzeichnis

Synlett 2014; 25(07): 1036-1040
DOI: 10.1055/s-0033-1340870

letter

Efficient Synthesis of Isoquinolines via Rh(III)-Catalyzed Oxidative Annulation of Picolinamides with Alkynes

Zhen-Chao Qian

^aDepartment of Chemistry, Zhejiang University, Hangzhou 310027, P. R. of China

,

Jun Zhou

^aDepartment of Chemistry, Zhejiang University, Hangzhou 310027, P. R. of China

,

Bo Li

^aDepartment of Chemistry, Zhejiang University, Hangzhou 310027, P. R. of China

,

Bing-Feng Shi*

^aDepartment of Chemistry, Zhejiang University, Hangzhou 310027, P. R. of China

^bState Key Laboratory of Bioorganic & Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science, Shanghai 200032, P. R. of China Fax: +86(571)87951895 eMail: bfshi@zju.edu.cn

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Abstract

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Abstract

An efficient synthesis of isoquinolines via Rh(III)-catalyzed oxidative annulation of picolinamides with alkynes using Cu(OAc)₂ as an oxidant has been developed. The scope of the reaction was studied with a selection of various picolinamides and alkynes, and the desired isoquinolines were obtained in good to excellent yields.

Key words

isoquinoline - rhodium(III) - C–H activation - pyridine - oxidative annulation

Volltext

Referenzen

References and Notes
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12 General Procedure for the Synthesis of Isoquinolines 3 via Oxidative Annulation of Picolinamides 1 with 2: N,N-Diethylpicolinamide (1; 0.2 mmol, 1.0 equiv), [Cp*RhCl₂]₂ (0.005 mmol, 2.5 mol%), AgSbF₆ (0.02 mmol, 10 mol%), Cu(OAc)₂ (0.4 mmol, 2.0 equiv), alkyne 2 (0.44 mmol, 2.2 equiv) and DCE (2 mL) were added to a 20-mL Schlenk tube. After being purged with nitrogen, the mixture was stirred at 120 °C for 24 h. Then concd aq NH₃ (2 mL) was added and stirred for 5 min. The resulting mixture was extracted with EtOAc. The organic layer was dried over Na₂SO₄, concentrated under reduced pressure and purified by chromatography on silica gel to afford isoquinoline 3. 5,6,7,8-Tetraphenylisoquinoline-1-carboxylic Acid Diethylamide (3a): Compound 3a was prepared in 92% yield according to the general procedure as a white solid. ¹H NMR (400 MHz, CDCl₃): δ = 0.91 (t, J = 7.2 Hz, 3 H), 1.21 (t, J = 6.8 Hz, 3 H), 2.60–2.69 (m, 1 H), 2.72–2.81 (m, 1 H), 2.95–3.04 (m, 1 H), 3.36–3.44 (m, 1 H), 6.59 (d, J = 6.8 Hz, 1 H), 6.75–6.86 (m, 9 H), 7.04–7.13 (m, 5 H), 7.20–7.27 (m, 5 H), 7.43 (d, J = 5.6 Hz, 1 H), 8.40 (d, J = 5.6 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 168.9, 156.5, 143.3, 142.5, 141.4, 139.7, 139.6, 138.3, 138.2, 138.1, 136.5, 133.5, 131.4, 131.3, 130.9, 130.8, 130.7, 130.6 (2 × C), 127.9, 127.2 (2 × C), 127.0, 126.9, 126.7, 126.5, 125.9, 125.7, 125.6, 124.0, 120.1, 77.5, 77.2, 76.8, 45.3, 40.1, 13.8, 13.7. HRMS (EI–TOF): m/z [M⁺] calcd for C₃₈H₃₂N₂O: 532.2515; found: 532.2511.

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Supporting Information

Efficient Synthesis of Isoquinolines via Rh(III)-Catalyzed Oxidative Annu­lation of Picolinamides with Alkynes

Efficient Synthesis of Isoquinolines via Rh(III)-Catalyzed Oxidative Annulation of Picolinamides with Alkynes