Palladium-Catalyzed Self-Coupling Reaction of Terminal Alkynes in the Presence of p-Chloranil: A Practical Method for the Synthesis of Triethynylethenes

Chao Chen; Zhezhe Ai; Jie Lin; Xiaoyin Hong; Chanjuan Xi

doi:10.1055/s-2006-950416

RSS-Feed abonnieren

Bitte kopieren Sie die angezeigte URL und fügen sie dann in Ihren RSS-Reader ein.

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

Teilen / Bookmarken

Facebook X Linkedin Weibo

PDF herunterladen

Synlett 2006(15): 2454-2458
DOI: 10.1055/s-2006-950416

LETTER

Palladium-Catalyzed Self-Coupling Reaction of Terminal Alkynes in the Presence of p-Chloranil: A Practical Method for the Synthesis of Triethynylethenes

Chao Chen, Zhezhe Ai, Jie Lin, Xiaoyin Hong, Chanjuan Xi*
Key Lab of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, P. R. of China
Fax: +86(10)62618239; e-Mail: cjxi@tsinghua.edu.cn;

Weitere Informationen

Publikationsverlauf

Received 18 May 2006
Publikationsdatum:
08. September 2006 (online)

Abstract
Volltext
Referenzen

Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

Pd-catalyzed reaction of aliphatic-1-alkynes in the presence of p-chloranil afforded triethynylethenes as exclusive self-coupling products in good yields. On the other hand, diynes were obtained when aromatic alkynes were used.

Key words

coupling reaction - alkyne - quinone - triethynylethene - palladium catalyst

References and Notes

1a Nielsen MB. Diederich F. Chem. Rev. 2005, 105: 1837

Crossref Google Scholar
1b Salaneck WR. Lundström I. Rånby B. Conjugated Polymers and Related Materials Oxford University Press; Oxford: 1993.

Crossref Google Scholar
1c Skotheim TA. Elsenbaumer RL. Reynold JR. Handbook of Conducting Polymers 2nd ed.: Marcel Dekker; New York: 1998.

Crossref Google Scholar
1d Kraft A. Grimsdale AC. Holmes AB. Angew. Chem. Int. Ed. 1998, 37: 402

Crossref Google Scholar
1e Pron A. Rannou P. Prog. Polym. Sci. 2002, 27: 135 ; and references therein

Crossref Google Scholar
2a Petty MC. Bryce MR. Bloor D. Introduction to Molecular Electronics Edward Arnold; London: 1995.

Crossref Google Scholar
2b Bumm LA. Arnold JJ. Cygan MT. Dunbar TD. Burgin TP. Jones L. Allara DL. Tour JM. Weiss PS. Science 1996, 271: 1705

Crossref Google Scholar
3 Gobbi L. Seiler P. Diederich F. Angew. Chem. Int. Ed. 1999, 38: 674

Crossref Google Scholar
4a Martin RE. Gubler U. Boudon C. Gramlich V. Bosshard C. Gisselbrecht J.-P. Günter P. Gross M. Diederich F. Chem. Eur. J. 1997, 3: 1505

Crossref Google Scholar
4b Spreiter R. Bosshard C. Knöpfle G. Günter P. Tykwinski RR. Schreiber M. Diederich F. J. Phys. Chem. B 1998, 102: 29

Crossref Google Scholar
4c Tykwinski RR. Gubler U. Martin RE. Diederich F. Bosshard C. Günter P. J. Phys. Chem. B 1998, 102: 4451

Crossref Google Scholar
5a Scott LT. Cooney MJ. In Modern Acetylene Chemistry Stang PJ. Diederich F. Wiley-VCH; Weinheim Germany: 1995. p.321

Crossref Google Scholar
5b Moore JS. Acc. Chem. Res. 1997, 30: 402

Crossref Google Scholar
5c Puddephatt RJ. Chem. Commun. 1998, 1055

Crossref Google Scholar
5d Youngs WJ. Tesseir CA. Bradshaw JD. Chem. Rev. 1999, 99: 3153

Crossref Google Scholar
5e de Meijere A. Kozhushkov SI. Top. Curr. Chem. 1999, 201: 1

Crossref Google Scholar
5f Haley MM. Park JJ. Brand SC. Top. Curr. Chem. 1999, 201: 81

Crossref Google Scholar
5g Bunz UHF. Top. Curr. Chem. 1999, 201: 131

Crossref Google Scholar
5h Tour JM. Acc. Chem. Res. 2000, 33: 791

Crossref Google Scholar
5i Hopf H. Classics in Hydrocarbon Chemistry Wiley-VCH; Weinheim Germany: 2000.

Crossref Google Scholar
5j Laskoski M. Roidl G. Smith MD. Bunz UHF. Angew. Chem. Int. Ed. 2001, 40: 1460

Crossref Google Scholar
5k Nielsen MB. Diederich F. Synlett 2002, 544

Crossref Google Scholar
5l Nielsen MB. Diederich F. Chem. Rec. 2002, 2: 189

Crossref Google Scholar
5m Camacho DH. Saito S. Yamamoto Y. J. Am. Chem. Soc. 2002, 124: 924

Crossref Google Scholar
6a Tykwinski RR. Diederich F. Liebigs Ann./Recl. 1997, 649

Crossref Google Scholar
6b Diederich F. Chem. Commun. 2001, 219

Crossref Google Scholar
7a Rossi R. Carpita A. Bigelli C. Tetrahedron Lett. 1985, 26: 523

Google Scholar
7b Rankin T. Tykwinski RR. Org. Lett. 2003, 5: 213

Google Scholar
7c Andersson AS. Qvortrup K. Torbensen ER. Mayer J.-P. Gisselbrecht J.-P. Boudon C. Gross M. Kadziola A. Kilså K. Nielsen MB. Eur. J. Org. Chem. 2005, 3600

Google Scholar
8a Reiser O. Angew. Chem. Int. Ed. 2006, 45: 2838

Google Scholar
8b Meijere A. Zezschwitz P. Brase S. Acc. Chem. Res. 2005, 38: 413

Google Scholar
8c Nicolaou KC. Bulger PG. Sarlah D. Angew. Chem. Int. Ed. 2005, 44: 4442

Google Scholar
8d Zeni G. Braga AL. Stefani HA. Acc. Chem. Res. 2003, 36: 731

Google Scholar
8e Culkin DA. Hartwig JF. Acc. Chem. Res. 2003, 36: 234

Google Scholar
8f Negishi E. Anastasia L. Chem. Rev. 2003, 103: 1979

Google Scholar
8g Amatore C. Jutand A. Acc. Chem. Res. 2000, 33: 314

Google Scholar
8h Zimmer R. Dinesh CU. Nandanan E. Khan FA. Chem. Rev. 2000, 100: 3067

Google Scholar
8i Beletskaya IP. Cheprakov AV. Chem. Rev. 2000, 100: 3009

Google Scholar
8j Crisp GT. Chem. Soc. Rev. 1998, 27: 427

Google Scholar
8k Miyaura N. Suzuki A. Chem. Rev. 1995, 95: 2457

Google Scholar
8l Stille JK. Angew. Chem., Int. Ed. Engl. 1986, 25: 508

Google Scholar
8m Heck RF. Org. React. (N.Y.) 1982, 27: 345

Google Scholar
9 Lei A. Srivastava M. Zhang X. J. Org. Chem. 2002, 67: 1969

Crossref PubMed Google Scholar
10 Liu Q. Burton DJ. Tetrahedron Lett. 1997, 38: 4371

Crossref Google Scholar
11 Vlassa M. Ciocan-Tarta I. Margineanu F. Oprean I. Tetrahedron 1996, 52: 1337

Crossref Google Scholar
12 Herrmann WA. Bohm VPW. Gstottmayr CWK. Grosche M. Reisinger C.-P. Weskamp T. J. Organomet. Chem. 2001, 617-618: 616

Crossref Google Scholar
13a Chen C. Xi C. Lai C. Wang R. Hong X. Eur. J. Org. Chem. 2004, 647

Crossref Google Scholar
13b Chen C. Xi C. Liu Y. Hong X. J. Org. Chem. 2006, 71: 5373

Crossref Google Scholar
NMR data for 5a-d were in accordance with literature values:
15a Organ MG. Ghasemi H. Valente C. Tetrahedron 2004, 60: 9453

Crossref Google Scholar
15b Damle SV. Seomoon D. Lee PH. J. Org. Chem. 2003, 68: 7085

Crossref Google Scholar
15c Rodríguez JG. Tejedor JL. Tetrahedron 2005, 61: 3033

Crossref Google Scholar
15d Loupy A. Meyer G. Tchoubar B. Tetrahedron 1978, 34: 1323

Crossref Google Scholar

14

Typical Reaction Procedure and Spectroscopic Data: To a solution of Pd(PPh₃)₄ (40 mg, 3.5 mmol%), CuCl (2 mg, 0.5 mmol%), 1-heptyne (525 µL, 4.0 mmol) in THF (6 mL), p-chloranil (1.0 mmol) and Et₃N (2.6 mmol, 0.4 mL) were added under a N₂ atmosphere. The mixture was allowed to stir at r.t. for 12 h, and quenched with 3 N HCl. The resulting solution was extracted with Et₂O and washed with a sat. NaCl solution. The combined Et₂O fractions were dried over Na₂SO₄ and concentrated under vacuum to yield the crude product. The crude product was purified by flash chromatography on silica gel using PE as the eluent. Removal of the solvent yielded 3a (342 mg) as a colorless liquid (90% isolated yield).
8-(Hept-1-ynyl)-9-pentylhexadeca-8-en-6,10-diyne (3a)
¹H NMR (CDCl₃/TMS, 300 MHz): δ = 0.88-0.93 (m, 12 H), 1.28-1.47 (m, 16 H), 1.51-1.62 (m, 8 H), 2.34-2.44 (m, 8 H). ¹³C NMR (CDCl₃/TMS, 75 MHz): δ = 14.0, 19.7, 19.7, 20.0, 22.3, 22.5, 27.9, 28.4, 28.5, 28.6, 31.1, 31.4, 34.6, 77.8, 79.3, 81.0, 92.5, 96.9, 100.9, 109.3, 138.1. GC-MS: m/z = 380. HRMS: m/z calcd for C₂₈H₄₄: 380.3443; found: 380.3441.
9-Hexyl-10-(oct-1-ynyl)octadeca-9-en-7,11-diyne (3b)
¹H NMR (CDCl₃/TMS, 300 MHz): δ = 0.85-0.89 (m, 12 H), 1.28 (d, J = 2.7 Hz, 16 H), 1.34-1.59 (m, 16 H), 2.33-2.42 (m, 8 H). ¹³C NMR (CDCl₃/TMS, 75 MHz): δ = 14.0, 19.7, 20.0, 22.5, 28.1, 28.5, 28.7, 28.7, 28. 8, 31.3, 31.4, 31.7, 34.6, 77.6, 79.1, 80.8, 92.5, 96.9, 100.9, 109.1, 138.1. GC-MS: m/z = 436. HRMS: m/z calcd for C₃₂H₅₂: 436.4069; found: 436.4071.
7-Butyl-8-(hex-1-ynyl)tetradeca-7-en-5,9-diyne (3c)
¹H NMR (CDCl₃/TMS, 300 MHz): δ = 0.86-0.93 (m, 12 H), 1.24-1.59 (m, 16 H), 2.34-2.43 (m, 8 H). ¹³C NMR (CDCl₃/TMS, 75 MHz): δ = 13.5, 13.5, 13.6, 13.8, 19.30, 19.4, 21.9, 22.2, 30.3, 30.6, 30.7, 30.8, 34.3, 77.7, 79.2, 80.9, 92.3, 96.8, 100.8, 109.1, 138.0. GC-MS: m/z = 324. HRMS: m/z calcd for C₂₄H₃₆: 324.2817; found: 324.2815.
6-(Pent-1-ynyl)-7-propyldodeca-6-en-4,8-diyne (3d) ¹H NMR (CDCl₃/TMS, 300 MHz): δ = 0.91 (t, J = 7.2 Hz, 3 H), 1.00 (q, J = 7.2 Hz, 9 H), 1.49-1.63 (m, 8 H), 2.31-2.41 (m, 8 H). ¹³C NMR (CDCl₃/TMS, 75 MHz): δ = 13.4, 13.6, 21.5, 21.6, 21.7, 22.0, 36.6, 77.8, 79.3, 81.0, 92.3, 96.8, 100.7, 109.2, 137.9. GC-MS: m/z = 268. HRMS: m/z calcd for C₂₀H₂₈: 268.2191; found: 268.2194.
5-Phenethyl-1,10-diphenyl-6-(4-phenylbut-1-ynyl)deca-5-en-3,7-diyne (3e)
¹H NMR (CDCl₃/TMS, 300 MHz): δ = 7.08-7.28 (m, 20 H), 2.57-2.90 (m, 16 H). ¹³C NMR (CDCl₃/TMS, 75 MHz): δ = 22.0, 22.0, 22.3, 34.4, 35.0, 35.2, 35.2, 36.5, 78.1, 79.6, 81.4, 92.4, 96.8, 100.9, 109.7, 126.0, 126.3, 126.4, 128.3, 128.4, 128.5, 128.5, 137.2, 140.5, 140.6, 140.7, 141.5. HRMS: m/z calcd for C₄₀H₃₆: 516.2817; found: 516.2820.
1,12-Dichloro-6-(5-chloropent-1-ynyl)-7-(3-chloro-propyl)dodeca-6-en-4,8-diyne (3f)
¹H NMR (CDCl₃/TMS, 300 MHz): δ = 1.95-2.08 (m, 8 H), 2.52-2.68 (m, 8 H), 3.52-3.75 (m, 8 H). ¹³C NMR (CDCl₃/TMS, 75 MHz): δ = 17.0, 17.2, 17.4, 31.2, 31.3, 31.8, 43.6, 43.6, 43.7, 44.3, 77.9, 79.7, 81.2, 91.2, 96.1, 99.7, 110.2, 136.5. GC-MS: m/z = 408. HRMS: m/z calcd for C₂₀H₂₄Cl₄: 404.0632; found: 404.0636.