PDF icon Download PDF
Synfacts 2014; 10(3): 0297
DOI: 10.1055/s-0033-1340750
Metal-Mediated Synthesis
© Georg Thieme Verlag Stuttgart · New York

Palladium-Catalyzed Linear-Selective Negishi Cross-Coupling of Allylzinc Halides

Contributor(s):
Paul Knochel
,
Nadja M. Barl
Yang Y, Mustard TJ. L, Cheong PH.-Y, * Buchwald SL. * Massachusetts Institute of Technology, Cambridge and Oregon State University, Corvallis, USA
Palladium-Catalyzed Completely Linear-Selective Negishi Cross-Coupling of Allylzinc Halides with Aryl and Vinyl Electrophiles.

Angew. Chem. Int. Ed. 2013;
52: 14098-14102
CrossrefPubMedSearch in Google Scholar
Further Information

Publication History

Publication Date:
17 February 2014 (online)

 
 PDF Download Permissions and Reprints

Key words

zinc - palladium - allylzinc halides - Negishi cross-coupling

Significance

Cheong, Buchwald, and co-workers report the first completely linear-selective ­palladium-catalyzed Negishi cross-coupling of various 3,3-disubstituted allylzinc reagents with (hetero)aryl and vinyl (pseudo)halides, leading to prenylated (hetero)aryl and alkenyl compounds in high yield and with excellent regioselectivity.


 

Comment

Apart from (hetero)aryl and vinyl bromides and chlorides, nonaflates and triflates were successfully used in this protocol. Computational studies reveal that an η1-α reductive elimination is preferred due to energetic reasons, leading exclusively to the prenylated products. Thus, the choice of catalyst and transmetalation reagent is crucial.


 

 


  Permissions and Reprints