Benzocycloheptynedicobalt Complexes by Intramolecular Nicholas Reactions

Yu Ding; James R. Green

doi:10.1055/s-2004-837215

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 2005(2): 271-274
DOI: 10.1055/s-2004-837215

LETTER

Benzocycloheptynedicobalt Complexes by Intramolecular Nicholas Reactions

Yu Ding, James R. Green*
Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario, N9B 3P4, Canada
Fax: +1(519)9737098; e-Mail: jgreen@uwindsor.ca;

Further Information

Publication History

Received 2 November 2004
Publication Date:
17 December 2004 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

Lewis acid mediated intramolecular Nicholas reactions of aryl (Z)-enyne propargyl acetate-Co₂(CO)₆ complexes 1 afford benzocycloheptenyne-Co₂(CO)₆ complexes 2 and their heterocyclic analogues.

Key words

Nicholas reactions - alkynes - arenes - complexes - transition metals

References

For recent reviews, see:
1a Green JR. Curr. Org. Chem. 2001, 5: 809

Crossref Google Scholar
1b Teobald BJ. Tetrahedron 2002, 58: 4133

Crossref Google Scholar
2a Lu Y. Green JR. Synlett 2001, 243

Crossref Google Scholar
2b Patel MM. Green JR. Chem. Commun. 1999, 509

Crossref Google Scholar
2c Green JR. Chem. Commun. 1998, 1751

Crossref Google Scholar
3a Tanino K. Onuki K. Asano K. Miyashita M. Nakamura T. Takahashi Y. Kuwajima I. J. Am. Chem. Soc. 2003, 125: 1498

Google Scholar
3b Tanino K. Kondo F. Shimizu T. Miyashita M. Org. Lett. 2002, 4: 2217

Google Scholar
3c Tanino K. Shimizu T. Miyama M. Kuwajima I. J. Am. Chem. Soc. 2000, 122: 6116

Google Scholar
3d Schreiber SL. Sammakia T. Crowe WE. J. Am. Chem. Soc. 1986, 108: 3128

Google Scholar
4a Young DGJ. Burlison JA. Peters U. J. Org. Chem. 2003, 68: 3494

Crossref Google Scholar
4b Green JR. Synlett 2001, 353

Crossref Google Scholar
4c Iwasawa N. Sakurada F. Iwamoto M. Org. Lett. 2000, 2: 871

Crossref Google Scholar
5 Iwasawa N. Satoh H. J. Am. Chem. Soc. 1999, 121: 7951

Crossref Google Scholar
For examples, see:
6a Uchiyama N. Kiuchi F. Ito M. Honda G. Takeda Y. Khodzhimatov OK. Ashurmetov OA. J. Nat. Prod. 2003, 66: 128

Crossref Google Scholar
6b Ulubelen A. Topcu G. J. Nat. Prod. 2000, 63: 879

Crossref Google Scholar
For examples, see:
7a Ulubelen A. Topcu G. Tan N. Lin L.-J. Cordell GA. Phytochemistry 1992, 31: 2419

Crossref Google Scholar
7b Purushothaman KK. Chandrasekharan S. Cameron AF. Connolly JD. Labbe C. Maltz A. Rycroft DS. Tetrahedron Lett. 1979, 979

Crossref Google Scholar
7c Lee J. Hong J. J. Org. Chem. 2004, 69: 6433

Crossref Google Scholar
8 Bentley KW. Nat. Prod. Rep. 2004, 21: 395 ; and references therein

Crossref PubMed Google Scholar
For examples, see:
9a Ho T.-L. Lin Y.-J. J. Chem. Soc., Perkin Trans. 1 1999, 1207

Crossref Google Scholar
9b Inoue M. Carson MW. Frontier AJ. Danishefsky SJ. J. Am. Chem. Soc. 2001, 123: 1878

Crossref Google Scholar
9c Asakawa Y. Toyota M. Tsunematsu T. Kubo I. Nakanishi K. Phytochemistry 1980, 19: 2147

Crossref Google Scholar
10 Ramirez F. Desai NB. McKelvie N. J. Am. Chem. Soc. 1962, 84: 1745

Crossref Google Scholar
11 Uenishi J. Kawahama R. Yonemitsu O. Tsuji J. J. Org. Chem. 1996, 63: 8965

Google Scholar
15 This reflects a tendency for a slightly lower preference for C-2 reactivity in thiophenes relative to furans and perhaps the known tendency for electron withdrawing C-3 groups to deactivate C-2 to a greater degree than C-4. See: Taylor R. In The Chemistry of Heterocyclic Compounds Part 2, Vol. 44: Gronowitz S. Wiley; New York: 1986. Chap. 1. p.16

Google Scholar
16 Brook MA. Silicon in Organic, Organometallic, and Polymer Chemistry Wiley and Sons; New York: 2000.

Google Scholar
18 Hosokawa S. Isobe M. Tetrahedron Lett. 1998, 39: 2609

Crossref Google Scholar

12

Selected compounds:
Compound 5b: IR (neat, KBr): ν_max = 3345, 3020, 2920, 2193 cm^-1. ¹H NMR: δ = 1.77 (1 H, br), 2.38 (3 H, s), 4.50 (1 H, d, J = 2.0 Hz), 5.71 (1 H, dt, J = 11.9, 2.0 Hz), 6.64 (1 H, d, J = 11.9 Hz), 7.11 (1 H, d, J = 7.5 Hz), 7.27 (1 H, dd, J = 7.7, 7.5 Hz), 7.63 (1 H, s), 7.68 (1 H, d, J = 7.7 Hz). ¹³C NMR: δ = 139.4, 137.8, 136.1, 129.4, 128.2, 125.6, 106.5, 93.6, 84.3, 51.8, 21.4. MS (EI): m/z = 172. HRMS (EI): m/z calcd for C₁₂H₁₂O: 172.0888; found: 172.0888.
Compound 5g: IR (neat, KBr): ν_max = 3358, 3097, 2918, 2191, 1699, 1602 cm^-1. ¹H NMR: δ = 2.39 (1 H, s), 4.51 (2 H, d, J = 2.0 Hz), 5.62 (1 H, dt, J = 11.7, 2.3 Hz), 6.70 (1 H, d, J = 11.7 Hz), 7.29 (1 H, dd, J = 4.9, 2.6 Hz), 7.62 (1 H, d, J = 5.0 Hz), 7.76 (1 H, d, J = 2.1 Hz). ¹³C NMR: δ = 138.3, 133.0, 127.7, 125.6, 125.2, 105.2, 93.8, 84.4, 51.6. MS (EI): m/z = 164. HRMS (EI): m/z calcd for C₉H₈OS: 164.0296; found: 164.0292.

13

Selected compounds:
Compound 1b: IR (neat, KBr): ν_max = 3014, 2927, 2092, 2024, 1748 cm^-1. ¹H NMR: δ = 2.03 (3 H, s), 2.39 (3 H, s), 4.52 (2 H, s), 6.61 (1 H, d, J = 11.0 Hz), 6.80 (1 H, d, J = 11.0 Hz), 7.02 (2 H, d, J = 8.2 Hz), 7.14 (1 H, d, J = 7.6 Hz), 7.29 (1 H, d, J = 7.5 Hz). ¹³C NMR: δ = 199.1 (br), 170.5, 138.2, 137.6, 132.5, 129.0, 128.5, 128.4, 127.5, 125.4, 91.4, 83.5, 64.9, 21.3, 20.3. MS (EI): m/z = 472 [M - CO]⁺, 444 [M - 2 CO]⁺, 416 [M -3 CO]⁺, 388 [M - 4 CO]⁺, 360 [M - 5 CO]⁺, 332 [M - 6CO]⁺. HRMS (EI): m/z calcd for C₂₀H₁₄ Co₂O₈: 443.9454 [M - 2 CO]⁺; found: 443.9457.
Compound 1g: IR (neat, KBr): ν_max = 3013, 2956, 2092, 2022, 1746 cm^-1. ¹H NMR: δ = 2.07 (3 H, s), 4.73 (2 H, s), 6.62 (1 H, d, J = 11.0 Hz), 6.67 (1 H, d, J = 11.0 Hz), 6.98 (1 H, d, J = 4.3 Hz), 7.13 (1 H, s), 7.38 (1 H, s). ¹³C NMR: δ = 199.3 (br), 170.5, 138.2, 128.3, 128.2, 126.8, 126.2, 123.4, 91.4, 83.3, 64.5, 20.3. MS (EI): m/z = 464 [M - CO]⁺, 436 [M - 2 CO]⁺, 408 [M - 3 CO]⁺, 380 [M - 4 CO]⁺, 352 [M - 5 CO]⁺, 324 [M - 6 CO]⁺. HRMS (EI): m/z calcd for C₁₇H₁₀Co₂O₈S: 435.8862 [M - 2 CO]⁺; found: 435.8853.

14

Experimental Procedure:
To a stirred ice cold solution of the propargyl acetate complex (0.2 mmol) in CH₂Cl₂ (20 mL) was added BF₃·OEt₂ (85.2 mg, 0.60 mmol) in CH₂Cl₂ (4 mL) over 10 min. After stirring at 0 °C for the time indicated in Table [2] , sat. NaHCO₃ solution was added, and the mixture was subjected to a conventional work up. Purification by flash chroma-tography afforded sequentially the benzocycloheptenyne complex and any recovered starting material.

17

Compound 2a: IR (neat, KBr): ν_max = 2929, 2091, 2021, 1574 cm^-1. ¹H NMR: δ = 4.18 (2 H, s), 6.77 (1 H, d, J = 10.1 Hz), 6.93 (1 H, d, J = 10.1 Hz), 7.22 (4 H, m). ¹³C NMR: δ = 199.3 (br), 137.5, 137.3, 133.1, 132.5, 129.4, 128.9, 128.8, 126.9, 102.3, 86.5, 40.8. MS (EI): m/z = 426 [M]⁺, 398 [M - CO]⁺, 370 [M - 2 CO]⁺, 342 [M - 3 CO]⁺, 314 [M - 4 CO]⁺, 286 [M - 5 CO]⁺, 258 [M - 6 CO]⁺. HRMS (EI): m/z calcd for C₁₇H₈Co₂O₆: 426.9063 [M + H]⁺; found: 426.9069.
Compound 2b: IR (neat, KBr): ν_max = 3014, 2858, 2090, 2053, 2021, 1557 cm^-1. ¹H NMR: δ = 2.31 (3 H, s), 4.14 (2 H, s), 6.72 (1 H, d, J = 10.1 Hz), 6.90 (1 H, d, J = 10.1 Hz), 7.00 (1 H, s), 7.07 (1 H, d, J = 7.9 Hz), 7.15 (1 H, d, J = 7.6 Hz); resonances for minor regioisomer (2b′) could be observed at δ = 2.51 (3 H, s), 4.10 (2 H, s), 6.82 (1 H, d, J = 10.0 Hz), 6.93 (1 H, d, J = 10.0 Hz), 7.03 (1 H, m), 7.10 (1 H, m), 7.17 (1 H, m). ¹³C NMR: δ = 199.4 (br), 137.3, 136.4, 134.5, 133.2, 129.6, 129.4, 128.5, 102.5, 86.9, 40.4, 20.7; resonances for the minor regioisomer could be observed at δ = 133.8, 130.7, 130.4, 128.8, 126.3, 34.2, 21.1. MS (EI): m/z = 440 [M]⁺, 412 [M - CO]⁺, 384 [M - 2 CO]⁺, 356 [M⁺ - 3 CO], 328 [M - 4 CO]⁺, 300 [M - 5 CO]⁺, 272 [M - 6 CO]⁺. HRMS (EI): m/z calcd for C₁₈H₁₀Co₂O₆: 439.9141; found: 439.9137.
Compound 2c: IR (neat, KBr): ν_max = 3014, 2956, 2837, 2090, 2050, 2020, 1604 cm^-1. ¹H NMR: δ = 3.77 (3 H, s), 4.10 (2 H, s), 6.68 (1 H, d, J = 10.1 Hz), 6.71 (1 H, s), 6.79 (1 H, d, J = 8.3 Hz), 6.92 (1 H, d, J = 10.1 Hz), 7.16 (1 H, d, J = 8.3 Hz). ¹³C NMR: δ = 199.3 (br), 158.3, 138.6, 132.8, 130.5, 130.0, 129.3, 117.7, 113.9, 102.9, 86.6, 55.3, 39.9. MS (EI): m/z = 456 [M]⁺, 428 [M - CO]⁺, 400 [M - 2 CO]⁺, 372 [M - 3 CO]⁺, 344 [M - 4 CO]⁺, 316 [M - 5 CO]⁺, 288 [M - 6 CO]⁺. HRMS (EI): m/z calcd for C₁₈H₁₀Co₂O₇: 455.9090; found: 455.9051.
Compound 2e: IR (neat, KBr): ν_max = 3026, 2935, 2090, 2052, 2022, 1602, 1556 cm^-1. ¹H NMR: δ = 3.88 (3 H, s), 5.35 (1 H, s), 6.77 (1 H, dd, J = 8.6, 2.6 Hz), 6.82 (1 H, s), 6.83 (1 H, m), 7.01 (1 H, d, J = 10.1 Hz), 7.09 (1 H, d, J = 8.5 Hz), 7.23 (1 H, m), 7.29 (2 H, m), 7.35 (2 H, m). ¹³C NMR: δ = 199.4 (br), 158.3, 144.4, 138.3, 133.5, 133.1, 131.3, 129.6, 128.6, 127.0, 118.4, 114.2, 107.1, 84.8, 55.4, 55.3. MS (EI): m/z = 504 [M - CO]⁺, 476 [M - 2 CO]⁺, 448 [M - 3 CO]⁺, 420 [ M - 4 CO]⁺, 392 [M - 5 CO]⁺, 364 [M - 6 CO]⁺. HRMS (EI): m/z calcd for C₂₄H₁₄Co₂O₇: 503.9454 [M - CO]⁺; found: 503.9437.
Compound 2f: IR (neat, KBr): ν_max = 3025, 2928, 2092, 2051, 2020. ¹H NMR: δ = 4.47 (2 H, s), 6.31 (1 H, s), 6.39 (1 H, d, J = 9.6 Hz), 6.57 (1 H, d, J = 9.6 Hz), 7.30 (1 H, s). ¹³C NMR: δ = 199.3 (br), 148.8, 140.8, 125.1, 124.1, 120.5, 113.3, 92.2, 86.6, 34.0. MS (EI): m/z = 416 [M]⁺, 388 [M - CO]⁺, 360 [M - 2 CO]⁺, 332 [M - 3 CO]⁺, 304 [M - 4 CO]⁺, 276 [M - 5 CO]⁺, 248 [M - 6 CO]⁺. HRMS (EI): m/z calcd for C₁₅H₆Co₂O₇: 415.8777 [M]⁺; found: 415.8752.
Compound 2g: IR (neat, KBr): ν_max = 2926, 2856, 2092, 2055, 2024, 1699, 1650, 1540 cm^-1. ¹H NMR: δ = 4.45 (2 H, s), 6.68 (1 H, AB quartet, J = 16.0 Hz), 6.74 (1 H, AB quartet, J = 16.1 Hz), 6.88 (1 H, d, J = 8.7 Hz), 7.08 (1 H, d, J = 8.8 Hz); resonances for minor regioisomer (2g′) could be observed (in CD₃CN) at δ = 4.34 (2 H, s), 6.66 (1 H, d, J = 9.9 Hz), 6.80 (1 H, d, J = 9.7 Hz), 7.20 (1 H, s), 7.38 (1 H, s). ¹³C NMR: δ = 199.1 (br), 136.8, 136.7, 132.0, 126.4, 126.2, 122.0, 97.6, 86.8, 34.6; resonances for the minor regioisomer could be observed at δ = 128.7, 126.9, 124.8, 35.5. MS (EI) m/z = 432 [M]⁺, 404 [M - CO]⁺, 376 [M - 2 CO]⁺, 348 [M - 3 CO]⁺, 320 [M - 4 CO]⁺, 292 [M - 5 CO]⁺, 264 [M - 6 CO]⁺. HRMS (EI): m/z calcd for C₁₅H₆Co₂O₆S: 403.8575 [M - CO]⁺; found: 403.8554.
Compound 2j: IR (neat, KBr): ν_max = 3055, 2090, 2051, 2021, 1594 cm^-1. ¹H NMR: δ = 3.78 (3 H, s), 3.83 (3 H, s), 3.91 (3 H, s), 4.05 (2 H, s), 6.62 (1 H, s), 6.93 (1 H, d, J = 10.4 Hz), 7.12 (1 H, d, J = 10.4 Hz). ¹³C NMR: δ = 199.4, 153.3, 152.8, 141.4, 134.3, 127.7, 125.9, 124.7, 108.4, 102.9, 87.7, 61.1, 61.0, 56.0, 41.1. MS (EI): m/z = 516 [M]⁺, 460 [M - 2 CO]⁺, 404 [M - 4 CO]⁺. HRMS: m/z calcd for C₂₀H₁₄Co₂O₉: 403.9505 [M - 4 CO]⁺; found: 403.9492.
Compound 2k: IR (neat, KBr): ν_max = 3014, 2957, 2360, 2091, 2052, 2022 cm^-1. ¹H NMR: δ = 0.28 (9 H, s), 4.20 (2 H, s), 6.76 (1 H, d, J = 10.1 Hz), 6.94 (1 H, d, J = 10.1 Hz), 7.16 (1 H, d, J = 7.5 Hz) 7.36 (1 H, s), 7.37 (1 H, d, J = 6.2 Hz). ¹³C NMR: δ = 199.4 (br), 142.0, 137.7, 136.3, 134.2, 133.2, 131.9, 131.7, 129.0, 102.4, 86.6, 40.9, -1.2. MS (EI) m/z = 498 [M]⁺, 470 [M - CO]⁺, 442 [M - 2 CO]⁺, 414 [M - 3 CO]⁺, 386 [M - 4 CO]⁺, 358 [M - 5 CO]⁺, 330 [M - 6 CO]⁺. HRMS (EI): m/z calcd for C₂₀H₁₆Co₂O₆Si: 469.9431 [M - CO]⁺; found: 469.9434.