Intramolecular Cyclocarbonylation of Cyclopropylidenyl Aldehydes Mediated by Molybdenum Carbonyl Complex

Chan-Mo Yu; Young-Taek Hong; Seok-Keun Yoon; Joon-Hwan Lee

doi:10.1055/s-2004-830849

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Synlett 2004(10): 1695-1698
DOI: 10.1055/s-2004-830849

LETTER

Intramolecular Cyclocarbonylation of Cyclopropylidenyl Aldehydes Mediated by Molybdenum Carbonyl Complex

Chan-Mo Yu*, Young-Taek Hong, Seok-Keun Yoon, Joon-Hwan Lee
Department of Chemistry and Lab for Metal-Catalyzed Reactions (NRL), Sungkyunkwan University, Suwon 440-746, Korea
Fax: +82(31)2907075; e-Mail: cmyu@chem.skku.ac.kr;

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Publication History

Received 9 April 2004
Publication Date:
15 July 2004 (online)

Abstract
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Abstract

A novel procedure for the synthesis of cis-bicyclic spirocyclopropanelactones from cyclopropylidenyl aldehydes via the molybdenum-mediated cyclocarbonylation is described. The use of (C₇H₈)Mo(CO)₃ with DMSO to promote the reaction results in an efficient and convenient protocol for the three-component assembly in high yields.

Key words

aldehydes - carbonyl complexes - cyclizations - cyclopropane - molybdenum

References

For excellent discussions, see:
1a Ojima I. Tzamarioudaki M. Li Z. Donovan R. Chem Rev. 1996, 96: 635

Search in Google Scholar
1b Lautens M. Klute W. Tam W. Chem. Rev. 1996, 96: 49

Search in Google Scholar
1c Trost BM. Toste FD. Pinkerton AB. Chem. Rev. 2001, 101: 2067

Search in Google Scholar
1d Aubert C. Buisine O. Malacria M. Chem. Rev. 2002, 102: 813

Search in Google Scholar
For general discussions, see:
2a Transition Metals for Organic Synthesis Vol I: Beller M. Bolm C. Wiley-VCH; Weinheim: 1998.
2b Transition Metals for Organic Synthesis Vol II: Beller M. Bolm C. Wiley-VCH; Weinheim: 1998.
3a Kablaoui NM. Buchwald SL. J. Am. Chem. Soc. 1995, 117: 6785

Crossref Search in Google Scholar
3b Kablaoui NM. Buchwald SL. J. Am. Chem. Soc. 1996, 118: 3182

Crossref Search in Google Scholar
3c Kablaoui NM. Hick FA. Buchwald SL. J. Am. Chem. Soc. 1996, 118: 5818

Crossref Search in Google Scholar
3d Kablaoui NM. Hick FA. Buchwald SL. J. Am. Chem. Soc. 1997, 119: 4424

Crossref Search in Google Scholar
4a Crowe WE. Vu AT. J. Am. Chem. Soc. 1996, 118: 1557

Crossref PubMed Search in Google Scholar
4b Mandal SM. Amin SR. Crowe WE. J. Am. Chem. Soc. 2001, 123: 6457

Crossref PubMed Search in Google Scholar
5 Trost BM. Acc. Chem. Res. 2002, 35: 695

Crossref PubMed Search in Google Scholar
6 Chatani N. Morimoto T. Fukumoto Y. Murai S. J. Am. Chem. Soc. 1998, 120: 5335

Search in Google Scholar
7a Yu C.-M. Yoon S.-K. Baek K. Lee J.-Y. Angew. Chem. Int. Ed. 1998, 37: 2392

Thieme Connect Search in Google Scholar
7b Yu C.-M. Kim Y.-M. Kim J.-M. Synlett 2003, 1518

Thieme Connect
8a Kang S.-K. Hong Y.-T. Lee J.-H. Kim W.-Y. Lee I. Yu C.-M. Org. Lett. 2003, 5: 2813

Crossref Search in Google Scholar
8b Kang S.-K. Kim K.-J. Hong Y.-T. Angew. Chem. Int. Ed. 2002, 41: 1584

Crossref Search in Google Scholar
8c Kang S.-K. Kim K.-J. Yu C.-M. Hwang J.-W. Do Y.-K. Org. Lett. 2001, 3: 2851

Crossref Search in Google Scholar
9 For a review see: Goti A. Cordero FM. Brandi A. In Small Ring Compounds in Organic Synthesis V de Meijere A. Springer; Berlin: 1996. p.1-98
10a Stolle A. Becker H. Salauen J. de Meijere A. Tetrahedron Lett. 1994, 35: 3521

Crossref Search in Google Scholar
10b Takano S. Inomata K. Ogasawara K. J. Chem. Soc., Chem. Commun. 1992, 169

Crossref
11 Ang KH. Braese S. Steinig AG. Meyer FE. Liebaria A. Voigt K. de Meijere A. Tetrahedron 1996, 52: 11503

Crossref Search in Google Scholar
12a Estieu K. Paugam R. Ollivier J. Salauen L. J. Org. Chem. 1997, 62: 8276

Crossref Search in Google Scholar
12b Ferrara M. Cordero FM. Goti A. Brandi A. Estieu K. Paugam R. Ollivier J. Salaun J. Eur. J. Org. Chem. 1999, 2725

Crossref
12c Pisaneschi F. Cordero FM. Goti A. Paugam R. Ollivier J. Brandi A. Salaun J. Tetrahedron: Asymmetry 2000, 11: 897

Crossref Search in Google Scholar
13 For a review see: Gibson SE. Stevenazzi A. Angew. Chem. Int. Ed. 2003, 42: 1800 ; and references cited therein

Crossref Search in Google Scholar
14a Jeong N. Lee SJ. Tetrahedron Lett. 1993, 34: 4027

Crossref Search in Google Scholar
14b Brummond KM. Kerekes AD. Wan H. J. Org. Chem. 2002, 67: 5156

Crossref Search in Google Scholar

15

General Procedure: A flame-dried sealed tube containing C₇H₈Mo(CO)₃ (152.0 mg, 0.56 mmol) was evacuated and carefully purged with argon three times and then charged with 3a (103.0 mg, 0.37 mmol) in dry toluene (3 mL). Freshly distilled DMSO (0.27 mL, 289 mg, 3.80 mmol) was then added at 20 °C. After stirring at 20 °C for 1 h, the reaction mixture was heated and allowed to proceed at 90 °C for 5 h. The resulting mixture was treated with EtOAc. The combined organics were washed with H₂O (3 ×) and brine (1 ×). The organic layer was dried over anhyd MgSO₄, filtered, and concentrated under reduced pressure. The crude product was purified by flash column chromatography (EtOAc-hexane, 1:1) to give 4a (83.0 mg, 0.27 mmol, 73%) as a colorless oil: R_f = 0.37 (EtOAc-hexane, 1:1).

16

¹H NMR and ¹³C NMR data: Compound 4a: ¹H NMR (500 MHz, CDCl₃): δ = 1.03 (dt, 2 H, J = 3.1, 5.6 Hz), 1.31 (dt, 2 H, J = 3.1, 8.2 Hz), 2.45 (s, 3 H), 2.82 (ddd, 1 H, J = 3.9, 8.2, 7.6 Hz), 3.06 (dd, 1 H, J = 7.6, 10.4 Hz), 3.19 (dd, 1 H, J = 3.9, 10.4 Hz), 3.22 (dd, 1 H, J = 5.3, 11.5 Hz), 3.61 (d, 1 H, J = 11.5 Hz), 5.06 (ddd, 1 H, J = 0.6, 5.3, 8.2 Hz), 7.35 (d, 2 H, J = 8.2 Hz), 7.69 (d, 2 H, J = 8.2 Hz). ¹³C NMR (125 MHz, CDCl₃): δ = 178.6, 144.6, 132.1, 130.1, 128.2, 79.7, 54.6, 52.3, 44.1, 24.8, 21.8, 18.4, 13.0. Compound 4b: ¹H NMR (500 MHz, CDCl₃): δ = 1.29 (d, 3 H, J = 6.7 Hz), 2.42 (s, 3 H), 2.42 (dd, 1 H, J = 3.7, 6.8 Hz), 3.73 (dq, 1 H, J = 3.7, 6.7 Hz), 3.74 (dd, 1 H, J = 4.5, 13.2 Hz), 3.86 (dd, 1 H, J = 0.8, 13.2 Hz), 5.01 (ddd, 1 H, J = 0.8, 4.5, 6.8 Hz), 7.30 (d, 2 H, J = 8.2 Hz), 7.70 (d, 2 H, J = 8.2 Hz). ¹³C NMR (125 MHz, CDCl₃): δ = 177.8, 144.3, 135.6, 130.1, 127.4, 80.3, 61.2, 53.3, 53.1, 25.4, 22.0, 21.8, 18.6, 12.2. Compound 4c: ¹H NMR (500 MHz, CDCl₃): δ = 0.83 (ddd, 1 H, J = 4.5, 7.3, 9.6 Hz), 1.03 (s, 3 H), 1.06 (ddd, 1 H, J = 4.5, 7.3, 10.1 Hz), 1.11 (ddd, 1 H, J = 4.5, 7.3, 9.6 Hz), 1.31 (ddd, 1 H, J = 4.5, 7.3, 10.1 Hz), 2.45 (s, 3 H), 2.97 (d, 1 H, J = 10.1 Hz), 3.09 (d, 1 H, J = 10.1 Hz), 3.45 (dd, 1 H, J = 1.7, 11.9 Hz), 3.58 (dd, 1 H, J = 5.3, 11.9 Hz), 4.56 (dd, 1 H, J = 1.7, 5.3 Hz), 7.35 (d, 2 H, J = 8.2 Hz), 7.68 (d, 2 H, J = 8.2 Hz). ¹³C NMR (125 MHz, CDCl₃): δ = 178.4, 144.5, 132.6, 130.1, 128.0, 86.2, 58.4, 53.7, 47.4, 28.9, 21.8, 20.6, 14.0, 12.3. Compound 4d: (major) ¹H NMR (500 MHz, CDCl₃): δ = 0.99 (m, 1 H), 1.05 (m, 2 H), 1.33 (m, 1 H), 1.45 (d, 3 H, J = 6.8 Hz), 2.44 (s, 3 H), 2.84 (ddd, 1 H, J = 5.6, 6.2, 7.9 Hz), 3.37 (dd, 1 H, J = 4.5, 7.9 Hz), 3.40 (dd, 1 H, J = 4.5, 6.2 Hz), 4.13 (dq, 1 H, J = 6.2, 7.3 Hz), 4.87 (dd, 1 H, J = 5.6, 7.3 Hz), 7.34 (d, 2 H, J = 8.2 Hz), 7.71 (d, 2 H, J = 8.2 Hz). ¹³C NMR (125 MHz, CDCl₃): δ = 178.7, 144.4, 133.7, 130.1, 127.5, 86.5, 62.1, 51.6, 43.6, 25.6, 21.8, 18.7, 17.9, 12.1. Compound 4d (minor) ¹H NMR (500 MHz, CDCl₃): δ = 0.88 (m, 1 H), 1.05 (m, 2 H), 1.18 (m, 1 H), 1.37 (d, 3 H, J = 6.7 Hz), 2.42 (s, 3 H), 2.63 (ddd, 1 H, J = 5.1, 6.5, 7.9 Hz), 3.19 (dd, 1 H, J = 7.9, 11.0 Hz), 3.20 (dd, 1 H, J = 5.1, 11.0 Hz), 3.68 (dq, 1 H, J = 6.7, 11.0 Hz), 4.66 (dd, 1 H, J = 6.5, 11.0 Hz), 7.31 (d, 2 H, J = 8.2 Hz), 7.69 (d, 2 H, J = 8.2 Hz). ¹³C NMR (125 MHz, CDCl₃): δ = 177.7, 144.3, 135.1, 130.1, 128.0, 82.8, 60.2, 52.6, 42.0, 24.9, 21.8, 18.2, 15.2, 12.8. Compound 4e: ¹H NMR (500 MHz, CDCl₃): δ = 1.05 (m, 2 H), 1.25 (t, 3 H, J = 7.0 Hz), 1.26 (t, 3 H, J = 7.0 Hz), 1.27 (m, 1 H), 1.35 (m, 1 H), 2.24 (dd, 1 H, J = 9.3, 13.8 Hz), 2.43 (dd, 1 H, J = 6.2, 13.8 Hz), 2.66 (dd, 1 H, J = 2.5, 14.9 Hz), 2.72 (dd, 1 H, J = 5.9, 14.9 Hz), 2.76 (ddd, 1 H, J = 6.2, 7.0, 9.3 Hz), 5.11 (ddd, 1 H, J = 2.5, 5.9, 7.0 Hz), 4.18 (q, 2 H, J = 7.0 Hz), 4.20 (q, 2 H, J = 7.0 Hz). ¹³C NMR (125 MHz, CDCl₃): δ = 179.5, 171.4, 170.7, 82.4, 62.2, 60.6, 44.8, 41.3, 38.7, 26.5, 18.9, 14.2, 12.7.