Transfer Hydrogenation of Isoquinolinium Salts Catalyzed by a Rhodium Complex

Jiashou Wu; Jian Liao; Jin Zhu; Jingen Deng

doi:10.1055/s-2006-949606

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synlett 2006(13): 2059-2062
DOI: 10.1055/s-2006-949606

LETTER

Transfer Hydrogenation of Isoquinolinium Salts Catalyzed by a Rhodium Complex

Jiashou Wu^a,b, Jian Liao^a, Jin Zhu*^a, Jingen Deng*^a
^a Key Laboratory of Asymmetric Synthesis & Chirotechnology of Sichuan Province and Union Laboratory of Asymmetric Synthesis, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China
Fax: +86(28)85223978; e-Mail: jgdeng@cioc.ac.cn;
^b Graduate School of Chinese Academy of Sciences, Beijing, P. R. of China

Further Information

Publication History

Received 12 April 2006
Publication Date:
09 August 2006 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

Regio- and chemoselective transfer hydrogenation of isoquinolinium salts catalyzed by [Cp*RhCl₂]₂ using HCOOH-Et₃N (5:2) as a hydrogen source was realized. A variety of N-methyl- and N-benzyl-1,2,3,4-tetrahydroisoquinoline alkaloids were obtained in high yields by the present catalyst system.

Key words

transfer hydrogenation - rhodium(III) complex - isoquinoline - isoquinolinium salt - tetrahydroisoquinoline

References and Notes

The reviews for synthesis of tetrahydroisoquinolines, see:
1a Chrzanowska M. Rozwadowska MD. Chem. Rev. 2004, 104: 3341

Crossref Google Scholar
1b Kaufman TS. Synthesis 2005, 339

Crossref Google Scholar
1c Rozwadowska MD. Heterocycles 1994, 39: 903

Crossref Google Scholar
1d Kaufman TS. Tetrahedron: Asymmetry 2004, 15: 1203

Crossref Google Scholar
For a comprehensive review, see:
2a Glorius F. Org. Biomol. Chem. 2005, 3: 4171 ; and references cited therein

Crossref PubMed Google Scholar
For catalytic hydrogenation via iminiums, see:
2b Glorius F. Spielkamp N. Holle S. Goddard R. Lehmann CW. Angew. Chem. Int. Ed. 2004, 43: 2850

Crossref PubMed Google Scholar
2c Legault CY. Charette AB. J. Am. Chem. Soc. 2005, 127: 8966

Crossref PubMed Google Scholar
2d Lu SM. Wang YQ. Han XW. Zhou YG. Angew. Chem. Int. Ed. 2006, 45: 2260

Crossref PubMed Google Scholar
3a Murahashi SI. Imada Y. Hirai Y. Tetrahedron Lett. 1987, 28: 77

Crossref Google Scholar
3b Murahashi SI. Imada Y. Hirai Y. Bull. Chem. Soc. Jpn. 1989, 62: 2968

Crossref Google Scholar
For the reviews of the transfer hydrogenation, see:
4a Brieger G. Nestrick TJ. Chem. Rev. 1974, 74: 567

Crossref PubMed Google Scholar
4b Johnstone RAW. Wilby AH. Entwistle ID. Chem. Rev. 1985, 85: 129

Crossref PubMed Google Scholar
4c Noyori R. Hashiguchi S. Acc. Chem. Res. 1997, 30: 97

Crossref PubMed Google Scholar
4d Gladiali S. Alberico E. Chem. Soc. Rev. 2006, 35: 226

Crossref PubMed Google Scholar
5 Fujita K. Kitatsuji C. Fulukawa S. Yamaguchi R. Tetrahedron Lett. 2004, 45: 3215

Crossref Google Scholar
6 Frediani P. Rosi L. Cetarini L. Frediani M. Inorg. Chim. Acta 2006, 359: 2650

Crossref Google Scholar
7a
No product was observed when isoquinoline was refluxed in MeCN catalyzed by [Cp*RhCl₂]₂ with 5:2 formic acid-Et₃N azeotropic mixture.

Crossref
7b Watanabe Y. Ohta T. Tsuji T. Hiyoshi T. Tsuji T. Bull. Chem. Soc. Jpn. 1984, 57: 2440

Crossref Google Scholar
8a Balczewski P. Joule JA. Synth. Commun. 1990, 20: 2815

Crossref Google Scholar
8b Derdau V. Tetrahedron Lett. 2004, 45: 8889

Crossref Google Scholar
8c Zacharie B. Moreau N. Dockendorff C. J. Org. Chem. 2001, 66: 5264

Crossref Google Scholar
9a Xue D. Chen YC. Cui X. Wang QW. Zhu J. Deng JG. J. Org. Chem. 2005, 70: 3584

Crossref Google Scholar
9b Ma Y. Liu H. Chen L. Cui X. Zhu J. Deng J. Org. Lett. 2003, 5: 2103

Crossref Google Scholar
9c Wang F. Liu H. Cun L. Zhu J. Deng J. Jiang Y. J. Org. Chem. 2005, 70: 9424

Crossref Google Scholar
9d Liu W. Cui X. Cun L. Wu J. Zhu J. Deng J. Tetrahedron: Asymmetry 2005, 16: 2525

Crossref Google Scholar
9e Chen YC. Wu TF. Deng JG. Liu H. Cui X. Jiang YZ. Choi MCK. Chan ASC. J. Org. Chem. 2002, 67: 5301

Crossref Google Scholar
9f Chen Y. Wu T. Jiang L. Deng J. Liu H. Zhu J. Jiang Y. J. Org. Chem. 2005, 70: 1006

Crossref Google Scholar
10 Wu J. Wang F. Ma Y. Cui X. Cun L. Zhu J. Deng J. Yu B. Chem. Commun. 2006, 1766

Crossref Google Scholar
11a Karimov A. Levkovich MG. Abdullaev ND. Shakirov R. Chem. Nat. Compd. 1994, 30: 331

Google Scholar
11b Karimov A. Shakirov R. Chem. Nat. Compd. 1994, 30: 335

Google Scholar

12

General Procedure.
To a solution of 1 (0.5 mmol) and [Cp*RhCl₂]₂ (0.0025 mmol) in CH₂Cl₂ (1.5 mL) under an atmosphere of argon was added a 5:2 formic acid-Et₃N azeotropic mixture (0.125 mL). The resulting mixture was stirred at 40 °C for a certain period of time, made basic by addition of aq Na₂CO₃, and then extracted with CH₂Cl₂. Purification on silicon gel afforded the desired products 2, which were characterized by ¹H NMR, ¹³C NMR and IR spectroscopy, and HRMS. The data of unknown compounds was shown as the following:
Compound 2a: colorless oil. IR: 3061, 3024, 2916, 2799, 1602, 1495, 1464, 1453, 739 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 2.80 (t, J = 5.9 Hz, 2 H), 2.96 (t, J = 5.8 Hz, 2 H), 3.70 (s, 2 H), 3.74 (br s, 2 H), 7.04 (br s, 1 H), 7.12-7.17 (m, 3 H), 7.31-7.47 (m, 5 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 29.1, 50.6, 56.1, 62.7, 125.5, 126.0, 126.5, 127.0, 128.2, 128.6, 129.0, 134.3, 134.8, 138.3 ppm. HRMS (ESI): m/z calcd for C₁₆H₁₇N [M + H]: 224.1434; found: 224.1443.
Compound 2b: colorless oil. IR: 3061, 3024, 2968, 2925, 2804, 1603, 1582, 1493, 1452, 1365, 757 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.48 (d, J = 6.7 Hz, 3 H), 2.74-2.83 (m, 2 H), 2.91-3.06 (m, 1 H), 3.13-3.16 (m, 1 H), 3.78 (d, J = 13.6 Hz, 1 H), 3.90 (d, J = 13.6 Hz, 1 H), 3.97 (q, J = 6.7 Hz, 1 H), 7.13-7.22 (m, 4 H), 7.33-7.49 (m, 5 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 19.7, 27.4, 43.8, 56.2, 58.2, 125.6, 125.8, 126.8, 127.4, 128.2, 128.7, 128.8, 134.3, 139.5, 140.4 ppm. HRMS (ESI): m/z calcd for C₁₇H₁₉N [M + H]: 238.1590; found: 238.1593.
Compound 2c: colorless oil. IR: 3058, 3024, 2991, 2930, 2867, 2830, 2803, 1607, 1513, 1492, 1462, 1353, 741 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.20 (d, J = 6.4 Hz, 3 H), 2.66 (dd, J = 5.8, 16.2 Hz, 1 H), 3.03-3.20 (m, 2 H), 3.62 (d, J = 13.2 Hz, 1 H), 3.66 (d, J = 15.7 Hz, 1 H), 3.75 (d, J = 15.8 Hz, 1 H), 3.87 (d, J = 13.2 Hz, 1 H), 6.90-7.00 (m, 1 H), 7.12-7.15 (m, 3 H), 7.29-7.44 (m, 5 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 15.1, 35.5, 51.5, 52.1, 57.2, 125.5, 126.0, 126.4, 126.9, 128.2, 128.8, 128.9, 134.0, 134.4, 139.4 ppm. HRMS (ESI): m/z calcd for C₁₇H₁₉N [M + H]: 238.1590; found: 238.1579.
Compound 2e: yellow oil. IR: 2921, 2832, 1610, 1575, 1524, 1452, 1465, 821, 800, 771, 733, 699 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 2.76 (t, J = 5.9 Hz, 2 H), 3.18 (t, J = 5.9 Hz, 2 H), 3.69 (s, 2 H), 3.70 (s, 2 H), 7.24-7.26 (m, 2 H), 7.29-7.41 (m, 5 H), 7.80-7.83 (m, 1 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 27.2, 49.9, 56.0, 62.5, 122.8, 126.1, 127.4, 128.4, 129.0, 130.3, 131.7, 137.6, 138.0 ppm. HRMS (ESI): m/z calcd for C₁₆H₁₇N₂O₂ [M + H]: 269.1285; found: 269.1281.
Compound 2g: light yellow oil. IR: 3058, 3024, 2991, 2929, 2867, 2830, 1607, 1513, 1492, 1462, 730 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 0.96 (t, J = 7.3 Hz, 3 H), 1.73-1.79 (m, 2 H), 2.46-2.54 (m, 1 H), 2.73-2.84 (m, 2 H), 3.13-3.18 (m, 1 H), 3.46 (t, J = 6.2 Hz, 1 H), 3.69 (d, J = 13.5 Hz, 1 H), 3.80 (d, J = 13.5 Hz, 1 H), 3.85 (s, 3 H), 3.87 (s, 3 H), 6.54 (s, 1 H), 6.59 (s, 1 H), 7.24-7.41 (m, 5 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 10.9, 24.2, 29.0, 43.6, 55.7, 55.9, 57.8, 61.9, 110.6, 111.2, 126.5, 126.7, 128.1, 128.8, 130.6, 140.0, 147.1 ppm. HRMS (ESI): m/z calcd for C₂₀H₂₅NO₂ [M + H]: 312.1958; found: 312.1968.
Compound 2h: light yellow oil. IR: 2950, 2904, 2867, 2831, 1608, 1513, 1463, 1375, 1358, 770 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 0.85 (d, J = 6.8 Hz, 3 H), 0.98 (d, J = 6.8 Hz, 3 H), 1.85-1.92 (m, 1 H), 2.42 (s, 3 H), 2.57-2.69 (m, 3 H), 3.09-3.17 (m, 2 H), 3.82 (s, 3 H), 3.83 (s, 3 H), 6.53 (s, 1 H), 6.56 (s, 1 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 20.0, 20.1, 25.4, 34.3, 44.1, 48.2, 55.7, 55.8, 69.4, 111.0, 111.8, 127.4, 128.7, 146.3, 147.0 ppm. HRMS (ESI): m/z calcd for C₁₅H₂₄NO₂ [M + H]: 250.1802; found: 250.1805.
Compound 2i: white solid; mp: 80-81 °C. IR: 3022, 2946, 2907, 2832, 1607, 1513, 1488, 1463, 1451, 1364, 741, 716 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 2.24 (s, 3 H), 2.57-2.65 (m, 1 H), 2.71-2.78 (m, 1 H), 3.06-3.22 (m, 2 H), 3.56 (s, 3 H), 3.85 (s, 3 H), 4.18 (s, 1 H), 6.09 (s, 1 H), 6.60 (s, 1 H), 7.22-7.34 (m, 5 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 28.9, 44.2, 52.2, 55.7, 71.0, 110.6, 111.4, 126.5, 127.3, 128.2, 129.5, 130.3, 143.8, 147.0, 147.3 ppm. HRMS (ESI): m/z calcd for C₁₈H₂₂NO₂ [M + H]: 284.1645; found: 284.1639.
Compound 2k: light yellow oil. IR: 3024, 2964, 2918, 2838, 1588, 1494, 1454, 1443, 1370, 735 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.17 (d, J = 6.1 Hz, 3 H), 2.42 (s, 3 H), 2.61-2.72 (m, 2 H), 2.80-2.88 (m, 1 H), 3.57 (d, J = 15.4 Hz, 1 H), 3.83 (d, J = 15.4 Hz, 1 H), 7.00-7.15 (m, 4 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 17.9, 36.7, 41.4, 54.8, 57.2, 125.5, 126.0, 128.4, 134.0, 134.4 ppm. HRMS (ESI): m/z calcd for C₁₁H₁₅N [M + H]: 162.1277; found: 162.1282.