Site-selective nitrenoid insertions utilizing postfunctionalized bifunctional rhodium(ii) catalysts

Abstract

Site-selective nitrenoid insertions are made possible with a postfunctionalized dirhodium(ii)-catalyst equipped with a remote hydrogen bonding site.

Heteronuclear Dirhodium-Gold Anionic Complexes: Polymeric Chains and Discrete Units

“…The properties and reactivity of these complexes and their derivatives make them very interesting compounds for the scientific community. Due to their potential applications, they have been studied in fields like catalysis [ 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 ], bioinorganic chemistry [ 13 , 14 , 15 , 16 , 17 ], metal organic frameworks (MOFs) [ 18 , 19 ], or gas absorption [ 20 , 21 ]. Metal-organic aerogels [ 22 , 23 ] and liquid crystals [ 24 , 25 ] can also be obtained using them as building blocks.…”

“…The structural diversity found in many of this kind of complexes must be also highlighted [ 12 , 20 , 21 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 ]. The axial sites of the paddlewheel structure are easily occupied by monodentate ligands, which has allowed the preparation of a large number of molecular compounds [ 1 , 2 , 34 , 35 , 36 , 37 ].…”

Site‐Selective Nitrene Transfer to Conjugated Olefins Directed by Oxazoline Peptide Ligands

“…[5] In most reports on diene aziridination, site-selectivity, if observed at all, has been a result of inherent selectivity. [8] On the basis of precedents for reactions catalyzed by peptidyl-copper complexes, [9,10] the use of amides as directing groups in aziridinations, [11] and for bis(oxazoline) ligands influencing the course of site-selective reactions, [12] we wondered whether short peptide sequences could be designed that would act as ligands for transition metals and thereby allow for achieving site-selective nitrene transfer as a function of noncovalent substrate-catalyst interactions. [7] In a related study, Schreiner and coworkers successfully designed a Rh II -catalyst for aziridination of the central olefinic position in a farnesol derivative, mediated through hydrogen bonding ( Figure 1B, II).…”

“…[7] In a related study, Schreiner and coworkers successfully designed a Rh II -catalyst for aziridination of the central olefinic position in a farnesol derivative, mediated through hydrogen bonding ( Figure 1B, II). [8] On the basis of precedents for reactions catalyzed by peptidyl-copper complexes, [9,10] the use of amides as directing groups in aziridinations, [11] and for bis(oxazoline) ligands influencing the course of site-selective reactions, [12] we wondered whether short peptide sequences could be designed that would act as ligands for transition metals and thereby allow for achieving site-selective nitrene transfer as a function of noncovalent substrate-catalyst interactions. With the aim of subsequent application in oligo-and polyene natural product functionalization, we were especially interested in conjugated olefin substrates ( Figure 1C).…”

“…, entry[7][8][9][10][11][12], which led to the identification of the Boc-Phe-[Ser]-[Ser]-NH-CHPh 2 sequence that resulted in good yield and selectivity greater than 1 : 5, favouring proximal functionalization. Notably, high levels of selectivity were maintained concomitant with only a slight decrease in yield at lowered catalyst loading(Figure 3B, entry 13) [24].…”