An unusual selectivity in Pd catalyzed cross coupling of terminal alkynes with 'unactivated' alkynes

Tetrahedron Letters

Volumn 38, Issue 18, 1997, Pages 3207-3210

  Trost, Barry M ^a   McIntosh, Matthias C ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; ALKYNE DERIVATIVE;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; IN VITRO STUDY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS;

EID: 0030970084     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)00614-X     Document Type: Article

References (18)

1. Trost, B.M. Angew. Chem., Int. Ed. Engl. 1995, 34, 259; Trost, B.M. Science 1991, 254, 1471.
2. Trost, B.M. Angew. Chem., Int. Ed. Engl. 1995, 34, 259; Trost, B.M. Science 1991, 254, 1471.
3. Trost, B.M.; Chan, C; Rühter, G. J. Am. Chem. Soc. 1987, 109, 3486.
4. For an overview of reactions involving insertion of a transition metal into a C-H bond of a terminal alkyne, see: Canty, A.J. in "Comprehensive Organometallic Chemistry," Able, E.W.; Stone, F.G.A.; Wilkinson, G.; Puddephatt, R.J. eds. Pergamon: Oxford, Vol. 9, Chapter 5, pp. 251-5. For some specific references wherein the transition metal is Pd, see: Dzhemilev, U.M.; Khusnutdinov, R.I.; Shchnadeva, N.A.; Nefedov, O.M.; Tolstikov, G.A. Bull. Acad. Sci. U.S.S.R. 1990, 2171; Selimov, F.A.; Rutman, O.G.; Dzhemilev, U.M. J. Org. Chem. 1988, 346, C58; Sabourin, E.T. J. Molec. Catal. 1984, 26, 363; Colthup, E.C.; Meriwether, L.S. J. Org. Chem. 1962, 27, 3930; Singer, H.; Wilkinson, G. J. Chem. Soc. (A), 1968, 190.
5. For an overview of reactions involving insertion of a transition metal into a C-H bond of a terminal alkyne, see: Canty, A.J. in "Comprehensive Organometallic Chemistry," Able, E.W.; Stone, F.G.A.; Wilkinson, G.; Puddephatt, R.J. eds. Pergamon: Oxford, Vol. 9, Chapter 5, pp. 251-5. For some specific references wherein the transition metal is Pd, see: Dzhemilev, U.M.; Khusnutdinov, R.I.; Shchnadeva, N.A.; Nefedov, O.M.; Tolstikov, G.A. Bull. Acad. Sci. U.S.S.R. 1990, 2171; Selimov, F.A.; Rutman, O.G.; Dzhemilev, U.M. J. Org. Chem. 1988, 346, C58; Sabourin, E.T. J. Molec. Catal. 1984, 26, 363; Colthup, E.C.; Meriwether, L.S. J. Org. Chem. 1962, 27, 3930; Singer, H.; Wilkinson, G. J. Chem. Soc. (A), 1968, 190.
6. For an overview of reactions involving insertion of a transition metal into a C-H bond of a terminal alkyne, see: Canty, A.J. in "Comprehensive Organometallic Chemistry," Able, E.W.; Stone, F.G.A.; Wilkinson, G.; Puddephatt, R.J. eds. Pergamon: Oxford, Vol. 9, Chapter 5, pp. 251-5. For some specific references wherein the transition metal is Pd, see: Dzhemilev, U.M.; Khusnutdinov, R.I.; Shchnadeva, N.A.; Nefedov, O.M.; Tolstikov, G.A. Bull. Acad. Sci. U.S.S.R. 1990, 2171; Selimov, F.A.; Rutman, O.G.; Dzhemilev, U.M. J. Org. Chem. 1988, 346, C58; Sabourin, E.T. J. Molec. Catal. 1984, 26, 363; Colthup, E.C.; Meriwether, L.S. J. Org. Chem. 1962, 27, 3930; Singer, H.; Wilkinson, G. J. Chem. Soc. (A), 1968, 190.
7. For an overview of reactions involving insertion of a transition metal into a C-H bond of a terminal alkyne, see: Canty, A.J. in "Comprehensive Organometallic Chemistry," Able, E.W.; Stone, F.G.A.; Wilkinson, G.; Puddephatt, R.J. eds. Pergamon: Oxford, Vol. 9, Chapter 5, pp. 251-5. For some specific references wherein the transition metal is Pd, see: Dzhemilev, U.M.; Khusnutdinov, R.I.; Shchnadeva, N.A.; Nefedov, O.M.; Tolstikov, G.A. Bull. Acad. Sci. U.S.S.R. 1990, 2171; Selimov, F.A.; Rutman, O.G.; Dzhemilev, U.M. J. Org. Chem. 1988, 346, C58; Sabourin, E.T. J. Molec. Catal. 1984, 26, 363; Colthup, E.C.; Meriwether, L.S. J. Org. Chem. 1962, 27, 3930; Singer, H.; Wilkinson, G. J. Chem. Soc. (A), 1968, 190.
8. For an overview of reactions involving insertion of a transition metal into a C-H bond of a terminal alkyne, see: Canty, A.J. in "Comprehensive Organometallic Chemistry," Able, E.W.; Stone, F.G.A.; Wilkinson, G.; Puddephatt, R.J. eds. Pergamon: Oxford, Vol. 9, Chapter 5, pp. 251-5. For some specific references wherein the transition metal is Pd, see: Dzhemilev, U.M.; Khusnutdinov, R.I.; Shchnadeva, N.A.; Nefedov, O.M.; Tolstikov, G.A. Bull. Acad. Sci. U.S.S.R. 1990, 2171; Selimov, F.A.; Rutman, O.G.; Dzhemilev, U.M. J. Org. Chem. 1988, 346, C58; Sabourin, E.T. J. Molec. Catal. 1984, 26, 363; Colthup, E.C.; Meriwether, L.S. J. Org. Chem. 1962, 27, 3930; Singer, H.; Wilkinson, G. J. Chem. Soc. (A), 1968, 190.
9. For an overview of reactions involving insertion of a transition metal into a C-H bond of a terminal alkyne, see: Canty, A.J. in "Comprehensive Organometallic Chemistry," Able, E.W.; Stone, F.G.A.; Wilkinson, G.; Puddephatt, R.J. eds. Pergamon: Oxford, Vol. 9, Chapter 5, pp. 251-5. For some specific references wherein the transition metal is Pd, see: Dzhemilev, U.M.; Khusnutdinov, R.I.; Shchnadeva, N.A.; Nefedov, O.M.; Tolstikov, G.A. Bull. Acad. Sci. U.S.S.R. 1990, 2171; Selimov, F.A.; Rutman, O.G.; Dzhemilev, U.M. J. Org. Chem. 1988, 346, C58; Sabourin, E.T. J. Molec. Catal. 1984, 26, 363; Colthup, E.C.; Meriwether, L.S. J. Org. Chem. 1962, 27, 3930; Singer, H.; Wilkinson, G. J. Chem. Soc. (A), 1968, 190.
10. Trost, B.M.; Sorum, M.T.; Chan, C.; Rühter, G. J. Am. Chem. Soc. 1997, 119, 698.
11. This compound has been fully characterized spectroscopically and the elemental composition established by high resolution mass spectroscopy and/or combustion analysis. All yields are for isolated product after flash column chromatography.
12. Cf. Ti catalyzed dimerization, see: Akita, M.; Yasuda, H.; Nakamura, A. Bull. Chem. Soc. Japan, 1984, 57, 480. Although the scope of the Ti catalyzed reaction, which shows a similar cross-coupling, was not fully evaluated, the sensitivity of the Ti catalyst to air or water and the need to protect hydroxyl groups indicates its lower chemoselectivity compared to Pd.
13. Guerriero, A.; Marchetti, F.; D'Ambrosio, M.; Senesi, S.; Dini, F.; Pietra, F. Helv. Chim. Acta 1993, 76, 855.
14. Nahm, S.; Weinreb, S.M. Tetrahedron Lett. 1981, 22, 3815. For a review, see: Sibi, M. Org. Prep. Proc. Int. 1993, 25, 15.
15. Nahm, S.; Weinreb, S.M. Tetrahedron Lett. 1981, 22, 3815. For a review, see: Sibi, M. Org. Prep. Proc. Int. 1993, 25, 15.
16. Evans, D.A.; Chapman, K.T.; Carreira, E.M. J. Am. Chem. Soc. 1988, 110, 3560.
17. Wolf, J. Werner, H.; Serhadli, O.; Ziegler, M.L. Angew. Chem., Int. Ed. Engl. 1983, 22, 414.
18. A nice example has appeared after completion of our work, see: Bach, J.; Berenguer, R.; Garcia, J.; Loscertale, T.; Manzanal, J.; Vilarrasa, J. Tetrahedron Lett. 1997, 38, 1091.