Alkynylation of Aryl Bromides with Propargylamines Catalyzed by a Palladium-Tetraphosphine Complex

Mhamed Lemhadri; Henri Doucet; Maurice Santelli

doi:10.1055/s-2005-865284

PAPER

Alkynylation of Aryl Bromides with Propargylamines Catalyzed by a Palladium-Tetraphosphine Complex

Mhamed Lemhadri, Henri Doucet*, Maurice Santelli*
UMR 6180 CNRS and Université d’Aix-Marseille III: ‘Chirotechnologies: catalyse et biocatalyse’, Laboratoire de Synthèse Organique, Faculté des Sciences de Saint Jérôme, Université d’Aix-Marseille III, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France
Fax: +33(4)91983865; e-Mail: henri.doucet@univ.u-3mrs.fr; e-Mail: m.santelli@univ.u-3mrs.fr;

Abstract

All articles of this category

Abstract

The tetraphosphine all-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane in combination with [Pd(C₃H₅)Cl]₂affords a very efficient catalyst for the alkynylation of aryl bromides with propargylamines. Higher reactions rates were observed with N,N-dialkylpropargylamines than with N-methylpropargylamine or propargylamine. A wide variety of substituents such as alkyl, phenyl, methoxy, dimethylamino, fluoro, trifluoromethyl, acetyl, benzoyl, formyl, carboxylate, nitro, or nitrile, on the aryl bromides are tolerated. High turnover numbers can be obtained with most of these aryl bromides. The coupling reaction of sterically very congested aryl bromides such as 9-bromoanthracene or 2,4,6-triisopropylbromobenzene also proceeds in good yields.

Key words

palladium - tetraphosphine - catalysis - alkynylation - propargylamine - aryl bromide

Full Text

References

<A NAME="RZ22104SS-1">1</A> Olivi N. Spruyt P. Peyrat J.-F. Alami M. Brion J.-D. Tetrahedron Lett. 2004, 45: 2607

For reviews on the palladium-catalyzed reaction of aryl halides with alkynes see:

<A NAME="RZ22104SS-2A">2a</A> Sonogashira K. Metal-Catalyzed Cross-Coupling Reactions Diederich F. Stang PJ. Wiley-VCH; New York: 1998.

<A NAME="RZ22104SS-2B">2b</A> Brandsma L. Vasilevsky SF. Verkruijsse HD. Application of Transition Metal Catalysts in Organic Synthesis Springer-Verlag; Berlin: 1998.

<A NAME="RZ22104SS-2C">2c</A> Sonogashira K. J. Organomet. Chem. 2002, 653: 46

For examples of efficient Pd-catalysts for the alkynylation of aryl halides:

<A NAME="RZ22104SS-3A">3a</A> Herrmann WA. Reisinger C.-P. Spiegler M. J. Organomet. Chem. 1998, 557: 93

<A NAME="RZ22104SS-3B">3b</A> Nakamura K. Okubo H. Yamaguchi M. Synlett 1999, 549

<A NAME="RZ22104SS-3C">3c</A> Herrmann WA. Böhm V. Reisinger C.-P. J. Organomet. Chem. 1999, 576: 23

<A NAME="RZ22104SS-3D">3d</A> McGuinness D. Cavell K. Organometallics 2000, 19: 741

<A NAME="RZ22104SS-3E">3e</A> Böhm VPW. Herrmann WA. Eur. J. Org. Chem. 2000, 3679

<A NAME="RZ22104SS-3F">3f</A> Hundertmark T. Littke A. Buchwald S. Fu G. Org. Lett. 2000, 2: 1729

<A NAME="RZ22104SS-3G">3g</A> Buchmeiser M. Schareina T. Kempe R. Wurst K. J. Organomet. Chem. 2001, 634: 39

<A NAME="RZ22104SS-3H">3h</A> Batey RA. Shen M. Lough AJ. Org. Lett. 2002, 4: 1411

<A NAME="RZ22104SS-3I">3i</A> Yang C. Nolan S. Organometallics 2002, 21: 1020

<A NAME="RZ22104SS-3J">3j</A> Alonso D. Najera C. Pacheco C. Tetrahedron Lett. 2002, 43: 9365

<A NAME="RZ22104SS-3K">3k</A> Méry D. Heuzé K. Astruc D. Chem. Commun. 2003, 1934

<A NAME="RZ22104SS-3L">3l</A> Köllhofer A. Pullmann T. Plenio H. Angew. Chem. Int. Ed. 2003, 42: 1056

<A NAME="RZ22104SS-3M">3m</A> Köllhofer A. Plenio H. Chem.-Eur. J. 2003, 9: 1416

<A NAME="RZ22104SS-3N">3n</A> Gelman D. Buchwald SL. Angew. Chem. Int. Ed. 2003, 42: 5993

<A NAME="RZ22104SS-3O">3o</A> Hierso J.-C. Fihri A. Amardeil R. Meunier P. Doucet H. Santelli M. Ivanov VV. Org. Lett. 2004, 6: 3473

For selected examples of Pd-catalyzed reaction of aryl iodides with propargylamine derivatives using PPh₃ as a ligand:

<A NAME="RZ22104SS-4A">4a</A> Gotteland J.-P. Dax C. Halazy S. Bioorg. Med. Chem. Lett. 1997, 7: 1153

<A NAME="RZ22104SS-4B">4b</A> Chaudhuri G. Kundu NG. J. Chem. Soc., Perkin Trans. 1 2000, 775

<A NAME="RZ22104SS-4C">4c</A> Kundu NG. Chaudhuri G. Tetrahedron 2001, 57: 6833

<A NAME="RZ22104SS-4D">4d</A> Nomak R. Snyder JK. Tetrahedron Lett. 2001, 42: 7929

<A NAME="RZ22104SS-4E">4e</A> Conn C. Shimmon R. Cordaro F. Hargraves T.-L. Ibrahim P. Bioorg. Med. Chem. Lett. 2001, 11: 2565

<A NAME="RZ22104SS-4F">4f</A> Kundu NG. Chaudhuri G. Upadhyay A. J. Org. Chem. 2001, 66: 20

<A NAME="RZ22104SS-4G">4g</A> Kundu NG. Nandi B. J. Org. Chem. 2001, 66: 4563

<A NAME="RZ22104SS-4H">4h</A> Nakamura H. Kamakura T. Ishikura M. Biellmann J.-F. J. Am. Chem. Soc. 2004, 126: 5958

For selected examples of Pd-catalyzed reaction of aryl bromides with propargylamine derivatives using PPh₃ as ligand:

<A NAME="RZ22104SS-5A">5a</A> Unroe MR. Reinhardt BA. Synthesis 1987, 981

<A NAME="RZ22104SS-5B">5b</A> Bleicher LS. Cosford NDP. Herbaut A. McCallum JS. McDonald IA. J. Org. Chem. 1998, 63: 1109

<A NAME="RZ22104SS-5C">5c</A> Inouye M. Fujimoto K. Furusyo M. Nakazumi H. J. Am. Chem. Soc. 1999, 121: 1452

<A NAME="RZ22104SS-5D">5d</A> Basak A. Shain JC. Khamrai K. Rudra KR. Basak A. J. Chem. Soc., Perkin Trans. 1 2000, 1955

<A NAME="RZ22104SS-6">6</A> Lopez-Deber MP. Castedo L. Granja JR. Org. Lett. 2001, 3: 2823

<A NAME="RZ22104SS-7">7</A> Laurenti D. Feuerstein M. Pèpe G. Doucet H. Santelli M. J. Org. Chem. 2001, 66: 1633

<A NAME="RZ22104SS-8">8</A> Feuerstein M. Laurenti D. Bougeant C. Doucet H. Santelli M. Chem. Commun. 2001, 325

<A NAME="RZ22104SS-9">9</A> Feuerstein M. Doucet H. Santelli M. J. Org. Chem. 2001, 66: 5923

<A NAME="RZ22104SS-10A">10a</A> Feuerstein M. Berthiol F. Doucet H. Santelli M. Org. Biomol. Chem. 2003, 1: 2235

<A NAME="RZ22104SS-10B">10b</A> Feuerstein M. Doucet H. Santelli M. Tetrahedron Lett. 2004, 45: 1630

<A NAME="RZ22104SS-10C">10c</A> Feuerstein M. Berthiol F. Doucet H. Santelli M. Synthesis 2004, 1281

<A NAME="RZ22104SS-10D">10d</A> Feuerstein M. Doucet H. Santelli M. Tetrahedron Lett. 2004, 45: 8443

<A NAME="RZ22104SS-11">11</A> Babayan AT. Chukhadzhyan EO. Chukhadzhyan EO. Zh. Org. Khim. 1973, 9: 467

<A NAME="RZ22104SS-12">12</A> Kwatra MM. Simon DZ. Salvador RL. Cooper PD. J. Med. Chem. 1978, 21: 253

<A NAME="RZ22104SS-13">13</A> Mannich C. Ber. Dtsch. Chem. Ges. B. 1933, 66: 418

<A NAME="RZ22104SS-14">14</A> Chukhadzhyan EO. Shakhatuni KG. Chukhadzhyan EH. Babayan AT. Arm. Khim. Zh. 1991, 44: 241

<A NAME="RZ22104SS-15">15</A> Kostrovskii VG. Shvartsberg MS. Andrievskii VN. Kotlyarevskii IL. Izv. Akad. Nauk, Ser. Khim. 1968, 2454

<A NAME="RZ22104SS-16">16</A> Izyumov EG. Norina OA. Andrievskaya EK. Fedenok LG. Kotlyarevskii IL. Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Biol. Med. Nauk 1968, 113

<A NAME="RZ22104SS-17">17</A> Dupont J. Basso NR. Meneghetti MR. Konrath RA. Burrow R. Horner M. Organometallics 1997, 16: 2386

<A NAME="RZ22104SS-18">18</A> Moody CJ. Rahimtoola KF. Porter B. Ross BC. J. Org. Chem. 1992, 57: 2105

<A NAME="RZ22104SS-19">19</A> Campi EM. Jackson WR. Nilsson Y. Tetrahedron Lett. 1991, 32: 1093