An Approach to the Synthesis of Enantiopure Tetrahydroisoquinoline via a Key Asymmetric Ugi Reaction

Li Pan; Ruijiao Chen; Dongshun Ni; Liang Xia; Xiaochuan Chen

doi:10.1055/s-0032-1317931

Synlett, Inhaltsverzeichnis

Synlett 2013; 24(2): 241-245
DOI: 10.1055/s-0032-1317931

letter

An Approach to the Synthesis of Enantiopure Tetrahydroisoquinoline via a Key Asymmetric Ugi Reaction

Li Pan

Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China Fax: +86(28)85413712 eMail: chenxc@scu.edu.cn

,

Ruijiao Chen

Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China Fax: +86(28)85413712 eMail: chenxc@scu.edu.cn

,

Dongshun Ni

Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China Fax: +86(28)85413712 eMail: chenxc@scu.edu.cn

,

Liang Xia

Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China Fax: +86(28)85413712 eMail: chenxc@scu.edu.cn

,

Xiaochuan Chen*

Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China Fax: +86(28)85413712 eMail: chenxc@scu.edu.cn

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Abstract

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Abstract

An approach to the synthesis of the multisubstituted tetrahydroisoquinoline featuring an asymmetric Ugi reaction of α-amino acid, aromatic aldehyde and an isocyanide has been developed. The promising utility of the strategy is demonstrated by a synthesis of an enantiopure functionalized 1,3-trans-tetrahydroisoquinolin-4-ol from natural l-valine. The configuration of the two stereocenters at C-1 and C-4, generated in the Ugi reaction and Pomeranz–Fritsch-type cyclization separately, was controlled very well and determined by NMR studies.

Key words

Ugi reaction - α-amino acid - aromatic aldehyde - tetrahydroisoquinoline - asymmetric synthesis

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Referenzen

References and Notes

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19 19: [α]_D ²⁰ +3 (c = 0.7, in CH₂Cl₂). IR (neat): 3498, 2954, 2928, 2859, 2710, 2610, 2252, 1608, 1510, 1462, 1343, 1311, 1251, 1221, 1152, 1108, 1046, 934, 838, 775, 666, 637 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 6.80 (s, 1 H), 6.77 (s, 1 H), 4.57 (br t, J = 6.2 Hz, 1 H), 3.99 (t, J = 5.8 Hz, 1 H), 3.89 (s, 3 H), 3.88 (s, 3 H), 3.86–3.88 (m, 2 H), 3.74 (dd, J = 5.8, 9.9 Hz, 1 H), 3.59 (d, J = 17.5 Hz, 1 H), 2.73 (dd, J = 2.4, 10.5 Hz, 1 H), 2.08–2.12 (m, 1 H), 1.59 (d, J = 2.9 Hz, 1 H), 1.10 (d, J = 4.5 Hz, 3 H), 1.09 (d, J = 4.6 Hz, 3 H), 0.85 (s, 9 H), 0.01 (s, 3 H), –0.04 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 149.0, 148.6, 129.1, 125.9, 118.8, 111.6, 111.1, 66.8, 64.8, 63.7, 62.2, 55.9, 38.7, 25.8, 20.3, 20.0, 18.1, –5.4, –5.6. HRMS (ESI⁺): m/z [M + H]⁺ calcd for C₂₃H₃₉N₂O₄Si: 435.2679; found: 435.2675.

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