Synthesis of Amido Esters and Amido Phosphonates through Carbonylation of Diazo Compounds Followed by Nucleophilic Addition Reaction

Abstract

We report a method to produce amido esters and amido phosphonates. Octacarbonyldicobalt [Co2(CO)8] was found to be an efficient nongaseous CO source that could be used as a reagent for the carbonylation of diazo esters and diazo phosphonates under mild reaction conditions. A number of diazo esters and diazo phosphonates smoothly underwent the reaction with CO, which was generated from Co2(CO)8, to produce the corresponding ketenes. The subsequent reaction with an amine afforded the expected amido esters and phosphonates. By applying the developed protocol, we synthesized a number of amido esters and amido phosphonates. Characterization of these compounds was achieved by using standard spectroscopic and analytical techniques as well as crystal structure analysis for four of the products.

Mechanistic insights into the SN2-type reactivity of aryl-Co(iii) masked-carbenes for C–C bond forming transformations

“… 30 , 31 , 35 Indeed, cobalt has recently been proved to be a practical metal to perform a vast array of transformations. Particularly, the use of carbene precursors has attracted recent interest due to their versatility as coupling partners in transformations such as carbonylation 36 , 37 and annulation, 38 – 44 including Co( iii )-radical-based outer-sphere functionalization ( Scheme 1a ). Regarding C–H functionalization, the field was pioneered by Miura using Co( ii ) salts.…”

Functionalization of Sulfonic Acid to Sulfonic Ester Using Diazo Compound under Mild Reaction Conditions in the Absence of Additives

“…By contrast, so far, Davies report of carbene insertion into the ‐OH bond of p‐tosyl sulfonic acid is the only known example in the literature for functionalization of the −OH bond of sulfonic acid. In this regard and in continuation of our research on carbene insertion reactions [67–72,81,83,86‐87] we herein report the insertion of carbene into the O−H bond of aromatic sulfonic acids using α‐diazo ester to generate the sulfonic esters.…”

“…insertion, cross coupling, cyclopropanation, cycloaddition and rearrangement [64–66] . In light of this, the carbene insertion into the X−H bonds has been utilized for the synthesis of α –amino, α –hydroxyl, α ‐silyl, or α –acyloxy ester derivatives [67–72] . Owing to its broad range of applicability and high reactivity, vanadyl bisacetylacetonate [VO(acac) 2 ] has proven to be a valuable catalyst in a wide range of organic transformations.…”

“…[64][65][66] In light of this, the carbene insertion into the XÀ H bonds has been utilized for the synthesis of α-amino, α-hydroxyl, α-silyl, or α-acyloxy ester derivatives. [67][68][69][70][71][72] Owing to its broad range of applicability and high reactivity, vanadyl bisacetylacetonate [VO(acac) 2 ] has proven to be a valuable catalyst in a wide range of organic transformations. Moreover, due to its low toxicity and solubility in organic solvents, handling becomes easier.…”

Synthesis of Diesters through Carbonylation of Diazo Compounds Followed by Alcohol Addition

“…Recently our research group reported the synthesis of amido esters and amido phosphonates by efficiently utilizing the ketene generated from the reaction of carbene from the diazo compounds and metal carbonyls . In continuation of this, herein we have report the synthesis of diesters by the carbonylation of carbene generated from phenyldiazoesters followed by nucleophilic addition of alcohol to the ketene.…”