Silver-Catalyzed C-H Insertion Reactions with Donor-Acceptor Diazoacetates

Abstract

In this paper we describe the first examples of carbene transfer with donor-acceptor diazoacetates and the silver tris(pyrazolyl)borate complex {HB[3,5-(CF 3 ) 2 Pz] 3 }Ag(THF). These reactions generally proceed in good yields and exhibit improved selectivities compared to simple diazoacetates.

Silver Carbenoids

“…19 This reaction has been extended to include donor-acceptor carbenes, and it was found to provide the expected products in most cases. 43 The Tp ð3;5-CF 3 Þ 2 Ag complex 22 and the related silver complex 33 were examined in C--H insertion reactions with several acyclic alkanes. 17,20,42 The chemical yields were excellent, and interestingly, both complexes exhibited relatively high proportions of C--H insertion at the primary carbon (Table 8.7).…”

The silver(I) complex [HB{3-(CF3),5-(CH3)Pz}3]AgNCCH3supported by a partially fluorinated scorpionate ligand

“…They are very useful in the stabilization of rare silver(I) complexes, such as [HB{3,5-(CF 3 ) 2 Pz} 3 ]AgCO (Dias & Jin, 1995), [HB{3,5-(CF 3 ) 2 Pz} 3 ]Ag(C 2 H 4 ), and [HB{3,5-(CF 3 ) 2 -Pz} 3 ]Ag(C 2 H 2 ) (Dias et al, 1997). Metal adducts of fluorinated tris(pyrazolyl)borates also feature more electrophilic metal sites and display greater catalytic activity in certain reactions, such as in C-H and C-halogen bond functionalization chemistry via carbene insertion, compared to the nonfluorinated electron-rich tris(pyrazolyl)borate analogs (Jayaratna, Pardue et al, 2013;Lovely et al, 2009;Dias & Lovely, 2008;Dias et al, 2004;Rangan et al, 2009;Díaz-Requejo & Pé rez, 2008). In this paper, we describe the synthesis and isolation of a silver(I)-acetonitrile adduct supported by the [HB{3-(CF 3 ),5-(CH 3 )Pz} 3 ] À ligand [see (2) in Scheme 1].…”

Partially fluorinated Scorpionate [HB(3-(CF3),5-(Ph)Pz)3]− as a supporting ligand for silver(I)-benzene, -carbonyl, and -PPh3 complexes

“…They display greater catalytic activity in certain reactions like in the C-H and C-halogen bond functionalization chemistry via carbene insertion, compared to the non-fluorinated, electron rich tris(pyrazolyl)borate analogs. [15,[22][23][24][25][26][27][28][29] [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49] In this paper, we describe the successful use of a mixed aryl-perfluoroalkyl substituent bearing tris(pyrazolyl)borate ligand in silver chemistry. In particular, we report the synthesis and complete characterization of Ag(I)-benzene, Ag(I)-carbonyl, (Figure 4).…”