The synthesis of 3,4,5-trisubstituted pyrazoles via a tandem catalytic cross-coupling/electrocyclization of enol triflates and diazoacetates is presented. The initial scope of this methodology is demonstrated on a range of differentially substituted acyclic and cyclic enol triflates as well as an elaborated set of diazoacetates to provide the corresponding pyrazoles with a high degree of structural complexity.

A practical and highly stereoselective iron-catalyzed cross-coupling reaction of stereodefined enol carbamates and Grignard reagents to yield tri- and tetrasubstituted acrylates is reported. A facile method for the stereoselective generation of these enol carbamates has also been developed.

Apractical and highly stereoselective iron-catalyzed cross-coupling reaction of stereodefined enol carbamates and Grignard reagents to yield tri-and tetrasubstituted acrylates is reported. Afacile method for the stereoselective generation of these enol carbamates has also been developed.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.

The FeCl3‐catalyzed cross‐coupling of E‐ and Z‐enol carbamates with Grignard reagents is reported to yield tri‐ and tetrasubstituted acrylates with retention of configuration.

Synthesis of Substituted Pyrazoles via Tandem Cross-Coupling/Electrocyclization of Enol Triflates and Diazoacetates. -A wide range of 3,4,5-trisubstituted pyrazoles is available. Interestingly, starting from tetrasubstituted enol triflates such as (VIII) and (XI) alkyl shift takes place giving pyrazoles like (IX), (X), and (XII). -(BABINSKI, D. J.; AGUILAR, H. R.; STILL, R.; FRANTZ*, D. E.; J. Org. Chem. 76 (2011) 15, 5915-5923, http://dx.doi.org/10.1021/jo201042c ; Dep. Chem., Univ. Tex., San Antonio, TX 78249, USA; Eng.) -Jannicke