Tunable 1,3-Lithium Shift of Propargylic/Allenylic Lithiums Formed by ­Conjugate Addition of 4-Aryl-3-butyn-1-enes with Organolithiums and the Subsequent Transmetalation/Pd(0)-Catalyzed Coupling Reaction with Aryl Halides

Abstract

A protocol was established to control the 1,3-lithium shift in propargylic/allenylic species formed by the conjugate addition of 4-aryl-3-butyn-1-enes with organolithiums. Subsequent transmetalation and Pd(0)-catalyzed cross-coupling with aryl halides afforded 1,1-diarylallenes and 1,3-diarylallenes, respectively, the structural diversities of which are determined by the easily availability of both 4-aryl-3-butyn-1-enes and the organolithium reagents.

conjugated enynes - organolithiums - conjugate addition - Negishi coupling - allenes

References

<A NAME="RU30804ST-1">1</A>

There are 22672 allene reactions summarized in Beilstein data.

<A NAME="RU30804ST-2A">2a</A> Allenes in Organic Synthesis   Schuter HF. Coppola GM. Wiley; New York: 1984. 

<A NAME="RU30804ST-2B">2b</A> The Chemistry of the Allenes   Landor SR. Academic Press; London: 1982. 

<A NAME="RU30804ST-2C">2c</A> The Chemistry of the Ketenes, Allenes and Related Compounds   Patai S. Wiley; Chichester: 1980. 

For some recent regioselective reactions of propargylic/allenylic species, see:

<A NAME="RU30804ST-3A">3a</A> Kjellgren J. Sundén H. Szabó K. J. Am. Chem. Soc.  2004,  126:  474 

<A NAME="RU30804ST-3B">3b</A> Yasuda M. Saito T. Ueba M. Baba A. Angew. Chem. Int. Ed.  2004,  43:  1414 

<A NAME="RU30804ST-3C">3c</A> Tokeshi BK. Tius MA. Synthesis  2004,  786 

<A NAME="RU30804ST-3D">3d</A> Nakamura H. Kamakura T. Ishikura M. Biellmann J.-F. J. Am. Chem. Soc.  2004,  126:  5958 

<A NAME="RU30804ST-3E">3e</A> Huang C.-W. Shanmugasundaram M. Chang H.-M. Cheng C.-H. Tetrahedron  2003,  59:  3635 

<A NAME="RU30804ST-3F">3f</A> Schultz-Fademrecht C. Wibbeling B. Fröhlich R. Hoppe D. Org. Lett.  2001,  3:  1221 

<A NAME="RU30804ST-3G">3g</A> Zimmermann M. Wibbeling B. Hoppe D. Synthesis  2004,  765 

<A NAME="RU30804ST-3H">3h</A> Hayashi T. Tokunaga N. Inoue K. Org. Lett.  2004,  6:  305 

For our own results, see:

<A NAME="RU30804ST-4A">4a</A> Ma S. Wang L. J. Org. Chem.  1998,  63:  3497 

<A NAME="RU30804ST-4B">4b</A> Ma S. Wang L. Chin. J. Chem.  1999,  17:  531 

<A NAME="RU30804ST-4C">4c</A> Ma S. Zhang A. J. Org. Chem.  1998,  63:  9601 

<A NAME="RU30804ST-4D">4d</A> Ma S. Zhang A. Yu Y. Xia W. J. Org. Chem.  2000,  65:  2287 

<A NAME="RU30804ST-4E">4e</A> Ma S. Zhang A. J. Org. Chem.  2002,  67:  2287 

<A NAME="RU30804ST-4F">4f</A> Ma S. Wang G. Angew. Chem. Int. Ed.  2003,  42:  4215 

<A NAME="RU30804ST-5">5</A> Ma S. He Q. Angew. Chem. Int. Ed.  2004,  43:  988 

<A NAME="RU30804ST-6A">6a</A> Petrov AA. Kormer VA. Savich IG. Zh. Obshch. Khim.  1960,  30:  3845 

<A NAME="RU30804ST-6B">6b</A> Ma S. Zhang J. Lu L. Chem. Eur. J.  2003,  7:  2447 

<A NAME="RU30804ST-6C">6c</A> Ma S. Yu S. Yin S. J. Org. Chem.  2003,  68:  8996