Efficient and Copper-Free Pd(OAc)2/DABCO-Catalyzed Sonogashira Cross-Coupling Reaction

Jin-Heng Li; Xu-Dong Zhang; Ye-Xiang Xie

doi:10.1055/s-2005-861805

PAPER

Efficient and Copper-Free Pd(OAc)₂/DABCO-Catalyzed Sonogashira Cross-Coupling Reaction

Jin-Heng Li*, Xu-Dong Zhang, Ye-Xiang Xie
Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, P. R. of China
Fax: +86(731)8872260; e-Mail: jhli@hunnu.edu.cn;

Abstract

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Abstract

An efficient and copper-free palladium-catalyzed Sonogashira cross-coupling reaction protocol is presented. In the presence of 3 mol% of Pd(OAc)₂ and 6 mol% of DABCO, cross-coupling of various aryl halides (iodides and bromides) with terminal alkynes afforded the corresponding alkynes in moderate to excellent yields. Moreover, high TONs (turnover numbers, up to 720 000 for the reaction of 1-iodo-4-nitrobenzene with phenylacetylene) for the Sonogashira cross-coupling reaction were observed.

Key words

Pd(OAc)₂/DABCO - Sonogashira cross-coupling reaction - aryl halide - terminal alkyne - turnover number

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References

1a Diederich F. Stang PJ. Metal-Catalyzed Cross-coupling Reactions Wiley-VCH; Weinheim: 1998.

1b Miyaura N. Cross-Coupling Reaction Springer; Berlin: 2002.

1c Negishi E. Handbook of Organopalladium Chemistry for Organic Synthesis Wiley-Interscience; New York: 2002.

1d Tykwinski RR. Angew. Chem. Int. Ed. 2003, 42: 1566

1e Tang S. Liang Y. Liu W.-J. Li J.-H. Chin. J. Org. Chem. 2004, 24: 1133

2a Viehe HG. Chemistry of Acetylene Marcel Dekker; New York: 1969. p.597

2b Bohlmann F. Burkhart FT. Zero C. Naturally Occurring Acetylenes Academic Press; London and New York: 1973.

2c Trahanovsky WS. Oxidation in Organic Chemistry Academic Press; New York: 1973.

2d Hansen L. Boll PM. Phytochem. 1986, 25: 285

2e Kim YS. Jin SH. Kim SL. Hahn DR. Arch. Pharm. Res. 1989, 12: 207

2f Matsunaga H. Katano M. Yamamoto H. Fujito H. Mori M. Tukata K. Chem. Pharm. Bull. 1990, 38: 3480

2g Hudlicky M. Oxidation in Organic Chemistry ACS Monograph 186; Washington DC: 1990. p.58

2h Sonogashira K. In Comprehensive Organic Synthesis Vol. 3: Trost BM. Fleming I. Pergamon; Oxford: 1991. p.551

2i Alonso F. Beletskaya IP. Yus M. Chem. Rev. 2004, 104: 3079

For recent representative papers on phosphine-palladium catalysts, see:

3a Böhm VPW. Herrmann WA. Eur. J. Org. Chem. 2000, 3679

3b Netherton MR. Fu GC. Org. Lett. 2001, 3: 4295

3c Méry D. Heuzé K. Astrc D. Chem. Commun. 2003, 1934

3d Gelman D. Buthwald SL. Angew. Chem. Int. Ed. 2003, 42: 5993

3e Elangovan A. Wang Y.-H. Ho T.-I. Org. Lett. 2003, 5: 1841

3f Feuerstein M. Berthiol F. Doucet H. Santelli M. Synthesis 2004, 1281 ; and references cited therein

3g Wolf C. Lerebours R. Org. Biomol. Chem. 2004, 2: 2161

3h Hierso J.-C. Fihri A. Amardeil R. Meunier P. Doucet H. Santelli M. Ivanov VV. Org. Lett. 2004, 6: 3473

3i Heuzé K. Méry D. Gauss D. Blais J.-C. Astruc D. Chem.-Eur. J. 2004, 10: 3936

3j Cheng J. Sun Y. Wang F. Guo M. Xu J.-H. Pan Y. Zhang Z. J. Org. Chem. 2004, 69: 5428

3k Feuerstein M. Doucet H. Santelli M. Tetrahedron Lett. 2004, 45: 8443

3l Adjabeng G. Brenstrum T. Frampton CS. Robertson AJ. Hillhouse J. McNulty J. Capretta A. J. Org. Chem. 2004, 69: 5082

3m Arques A. Aunon D. Molina P. Tetrahedron Lett. 2004, 45: 4337

For recent representative papers on other phosphine-free ligand-palladium catalysts, see:

4a Loch JA. Albrecht M. Peris E. Mata J. Faller JW. Crabtree RH. Organometallics 2002, 21: 700

4b Herrmann WA. Angew. Chem. Int. Ed. 2002, 41: 1290

4c Batey RA. Shen M. Lough AJ. Org. Lett. 2002, 4: 1411

4d Eckhardt M. Fu GC. J. Am. Chem. Soc. 2003, 125: 13642

4e Yong BS. Nolan SP. Chemtracts: Org. Chem. 2003, 205

4f Rau S. Lamm K. Goerls H. Schoeffel J. Walther D. J. Organomet. Chem. 2004, 689: 3582

4g Gossage RA. Jenkins HA. Yadav PN. Tetrahedron Lett. 2004, 45: 7689

4h Alonso DA. Botella L. Najera C. Pacheco MC. Synthesis 2004, 1713

4i Thakur VV. Kumar NSCR. Sudalai A. Tetrahedron Lett. 2004, 45: 2915

For recent representative papers on ligand-free palladium catalysts, see:

5a Alami M. Ferri F. Linstrumelle G. Tetrahedron Lett. 1993, 34: 6403

5b Heidenreich RG. Kohler K. Krauter JGE. Pietsch J. Synlett 2002, 1118

5c Urgaonkar S. Verkade JG. J. Org. Chem. 2004, 69: 5752 ; and references cited therein

5d Son SU. Jang Y. Park J. Na HB. Park HM. Yun HJ. Lee J. Hyeon T. J. Am. Chem. Soc. 2004, 126: 5026

6a Homogeneous Catalysis with Metal Phosphine Complexes Pignolet LH. Plenum; New York: 1983.

6b Parshall GW. Ittel S. Homogeneous Catalysis Wiley; New York: 1992.

7 Siemsen P. Livingston RC. Diederich F. Angew. Chem. Int. Ed. 2000, 39: 2632

8 Li J.-H. Liu W.-J. Org. Lett. 2004, 6: 2809

Among the tertiary amines, only HMPA is bulkier than DABCO. In the coupling transformation, although bulk favors reductive elimination, it impedes oxidative addition and transmetalation of substrates allowed by the more flexible ligand, see:

9a Strieter ER. Blackmond DG. Buchwald SL. J. Am. Chem. Soc. 2003, 125: 13978

9b See also: Altenhoff G. Goddard R. Lehmann CW. Glorius F. Angew. Chem. Int. Ed. 2003, 42: 3690

9c Tao B. Boykin DW. J. Org. Chem. 2004, 69: 4330

10 Arques A. Auñon A. Molina P. Tetrahedron Lett. 2004, 45: 4337 ; and references cited therein