Structural and Mechanistic Insights into s‐Block Bimetallic Catalysis: Sodium Magnesiate‐Catalyzed Guanylation of Amines. Issue 49 (27th October 2016)

• Record Type: Journal Article
• Authors: De Tullio, Marco; Hernán‐Gómez, Alberto; Livingstone, Zoe; Clegg, William; Kennedy, Alan R.; Harrington, Ross W.; Antiñolo, Antonio; Martínez, Antonio; Carrillo‐Hermosilla, Fernando; Hevia, Eva
• Is Part Of: Chemistry. Volume 22:Issue 49(2016)
• Page Start: 17646
• Page End: 17656
• Publication Date: 2016-10-27
• Subjects: cooperative effects -- guanidines -- homogeneous catalysis -- magnesiates -- s-block metals; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201602906
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: To advance the catalytic applications of s‐block mixed‐metal complexes, sodium magnesiate [NaMg(CH2 SiMe3 )3 ] (1 ) is reported as an efficient precatalyst for the guanylation of a variety of anilines and secondary amines with carbodiimides. First examples of hydrophosphination of carbodiimides by using a Mg catalyst are also described. The catalytic ability of the mixed‐metal system is much greater than that of its homometallic components [NaCH2 SiMe3 ] and [Mg(CH2 SiMe3 )2 ]. Stoichiometric studies suggest that magnesiate amido and guanidinate complexes are intermediates in these catalytic routes. Reactivity and kinetic studies imply that these guanylation reactions occur via (tris)amide intermediates that react with carbodiiimides in insertion steps. The rate law for the guanylation of N, N ′‐diisopropylcarbodiimide with 4‐ tert ‐butylaniline catalyzed by1 is first order with respect to [amine], [carbodiimide], and [catalyst], and the reaction shows a large kinetic isotopic effect, which is consistent with an amine‐assisted rate‐determining carbodiimide insertion transition state. Studies to assess the effect of sodium in these transformations denote a secondary role with little involvement in the catalytic cycle. Abstract : Magnesium activATES : Showing enhanced catalytic ability compared with their homometallic components (see figure), mixed Na/Mg complexes effectively catalyze the guanylation of a range of amines under mild reaction conditions, the key for which is the anionic activation of magnesium after installation within a sodium magnesiate platform.