A Novel One-Pot Iridium-Catalyzed Alder-Ene-Murahashi Sequence

Manuela Kummeter; Christian M. Ruff; Thomas J. J. Müller

doi:10.1055/s-2007-970753

LETTER

A Novel One-Pot Iridium-Catalyzed Alder-Ene-Murahashi Sequence

Manuela Kummeter, Christian M. Ruff, Thomas J. J. Müller*
Organisch-Chemisches Institut der Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Fax: +49(211)8114324; e-Mail: ThomasJJ.Mueller@uni-duesseldorf.de;

Abstract

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Abstract

Yne allyl alcohols could be transformed under very mild conditions by a novel iridium-catalyzed one-pot cycloisomerization-Murahashi sequence in 43-77% yield.

Key words

additions - alkynes - catalysis - condensations - ene reactions - iridium

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References

References and Notes

1

New address: Lehrstuhl für Organische Chemie, Institut für Organische Chemie und Makromolekulare Chemie der Heinrich-Heine-Universität Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf, Germany

For reviews, see:

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2b Ajamian A. Gleason JL. Angew. Chem. Int. Ed. 2004, 43: 3754

2c Lee JM. Na Y. Han H. Chang S. Chem. Soc. Rev. 2004, 33: 302

3 For a review on sequentially Pd-catalyzed reactions, see: Müller TJJ. Top. Organomet. Chem. 2006, 19: 149

4a For a review on sequentially Ru-catalyzed reactions, see: Bruneau C. Dérien S. Dixneuf PH. Top. Organomet. Chem. 2006, 19: 296

4b For a highlight on sequentially Rh-catalyzed reactions, see: Körber N. Müller TJJ. Chim. Oggi 2006, 24: 22

For representative transition-metal-catalyzed Alder-ene reactions, see for example Pd:

5a Trost BM. Acc. Chem. Res. 1990, 23: 34

5b Trost BM. Janssen Chim. Acta 1991, 9: 3

5c Trost BM. Krische MJ. Synlett 1998, 1

Ru:

5d Trost BM. Chem. Ber. 1996, 129: 1313

5e Trost BM. Toste FD. Tetrahedron Lett. 1999, 40: 7739

Rh:

5f Cao P. Wang B. Zhang X. J. Am. Chem. Soc. 2000, 122: 6490

5g Cao P. Zhang X. Angew. Chem. Int. Ed. 2000, 22: 4104

5h Lei A. He M. Zhang X. J. Am. Chem. Soc. 2002, 124: 8198

5i Hashmi ASK. Haufe P. Rivas Nass A. Bats JW. Adv. Synth. Catal. 2004, 346: 421

5j Hashmi ASK. Haufe P. Rivas Nass A. Adv. Synth. Catal. 2003, 345: 1237

5k Hashmi ASK. Karch R. Rivas Nass A. Chem. Today 2006, 24: 16 ; supplement

Ir:

5l Chatani N. Inoue H. Morimoto T. Muto T. Murai S. J. Org. Chem. 2001, 66: 4433

5m Kezuka S. Okado T. Niou E. Takeuchi R. Org. Lett. 2005, 7: 1711

Ti:

5n Sturla SJ. Kablaoui NM. Buchwald SL. J. Am. Chem. Soc. 1999, 121: 1976

6a Bartels B. Helmchen G. Chem. Commun. 1999, 8: 741

6b Schelwies M. Dübon P. Helmchen G. Angew. Chem. Int. Ed. 2006, 45: 2466

7 Murahashi S.-I. Takaya H. Acc. Chem. Res. 2000, 33: 1855

8a Kressierer CJ. Müller TJJ. Synlett 2004, 655

8b Kressierer CJ. Müller TJJ. Tetrahedron Lett. 2004, 45: 2155

8c Kressierer CJ. Müller TJJ. Org. Lett. 2005, 7: 2237

8d Kressierer CJ. Müller TJJ. Synlett 2005, 1721

9

All compounds have been fully characterized by spectroscopic methods and by correct elemental analysis or HRMS.

10

Typical Procedure of Compound 2c (Table 1, Entry 6).
To a solution of 30 mg (44 µmol) of [IR (COD)Cl]₂ in 5 mL of anhyd THF were added 252 mg (1.02 mmol) of 1c. The reaction mixture was stirred at 60 °C for 24 h before it was diluted with Et₂O. After quick chromatography on dry silica gel, 179 mg (71%) of 2c were obtained as a yellow solid; mp 61-66 °C. R _f = 0.40 (n-hexane-Et₂O = 10:90, SiO₂). ¹H NMR (300 MHz, CDCl₃): δ = 2.79 (dd, J = 8.4, 18.4 Hz, 1 H), 2.91 (dd, J = 5.1, 18.4 Hz, 1 H), 3.42 (m, 1 H), 3.61 (dd, J = 5.6, 8.8 Hz, 1 H), 4.16 (dd, J = 6.7, 8.8 Hz, 1 H), 4.66 (s, 2 H), 6.46 (s, 1 H), 7.26 (d, J = 8.7 Hz, 2 H), 8.20 (d, J = 8.8 Hz, 2 H), 9.88 (s, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 39.8 (CH), 47.3 (CH₂), 69.9 (CH₂), 72.4 (CH₂), 119.8 (CH), 123.9 (CH), 128.4 (CH), 143.2 (C_quat), 146.1 (C_quat), 149.3 (C_quat), 199.9 (CH). MS (EI, 70 eV): m/z (%) = 247 (24) [M]⁺, 230 (38) [M - OH]⁺, 229 (33) [M - H₂O]⁺, 204 (31) [M - C₂H₃O]⁺, 203 (64) [M - C₂H₄O]⁺, 158 (22) [M - C₄H₁₀O]⁺. HRMS (EI): m/z calcd: 247.0845; found: 247.0822. Anal. Calcd for C₁₃H₁₃O₄N (247.3): C, 63.15; H, 5.30; N 5.66. Found: C, 62.99; H, 5.39; N, 5.52.

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CCDC-630817 (2c) and CCDC-630818 (4e) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 (1223)336033; or deposit@ccdc.cam.ac.uk].

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Typical Procedure for 4e (Table 2, Entry 8).
To a solution of 30 mg (44 µmol) of [IR (COD)Cl]₂ in 2.5 mL of anhyd THF were added 360 mg (1.01 mmol) of 1e. The reaction mixture was stirred at r.t. for 24 h. Then 150 mg (1.51 mmol) of cyanoacetate were added and the reaction mixture was stirred for another 24 h at r.t. After dilution with Et₂O the crude product was chromatographed on silica gel to give 319 mg (0.73 mmol, 72%) of 4e as a white crystalline solid; mp 166-166.5 °C. R _f = 0.37 (n-hexane-Et₂O = 10:90, SiO₂). ¹H NMR (300 MHz, CDCl₃): δ = 2.42 (s, 3 H), 2.72 (m, 1 H), 2.85 (ddd, J = 6.1, 7.7, 13.9 Hz, 1 H), 2.99-3.11 (m, 2 H), 3.41 (ddd, J = 2.2, 8.2, 8.3 Hz, 1 H), 3.87 (s, 3 H), 4.23-4.05 (m, 2 H), 6.31 (s, 1 H), 7.14 (d, J = 8.4 Hz, 2 H), 7.43-7.21 (m, 5 H), 7.63 (dd, J = 7.9 Hz, 1 H), 7.72 (d, J = 8.3 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 21.5 (CH₃), 35.1 (CH₂), 43.4 (CH), 50.3 (CH₂), 51.6 (CH₂), 53.3 (CH₃), 111.4 (C_quat), 113.3 (C_quat), 124.8 (CH), 127.6 (CH), 127.7 (CH), 128.2 (CH), 128.7 (CH), 129.9 (CH), 132.5 (C_quat), 135.7 (C_quat), 137.6 (C_quat), 144.0 (C_quat), 159.4 (CH), 161.2 (C_quat.). MS (EI, 70 eV): m/z (%) = 436 (18) [M]⁺, 312 (54) [M - C₆H₆NO₂]⁺, 282 (25) [M -C₇H₆O₂S]⁺, 281 (100) [M - C₇H₇O₂S]⁺, 157 (25), 149 (25), 156 (60) [C₁₁H₁₀N]⁺, 91 (35) [C₇H₇]⁺. Anal. Calcd for C₂₄H₂₄O₄N₂S (436.5): C, 66.04; H, 5.54; N, 6.42. Found: C, 65.95; H, 5.66; N, 6.35.