Silver(I)-catalyzed asymmetric aldol reaction of isocyanoacetate

Catalytic Isonitrile Insertions and Condensations Initiated by RNC–X Complexation

“…Silver-ferrocenyl catalysts condense methyl isocyanoacetate ( 11a ) [60] and tosylmethyl isocyanide ( 49a ) [61] with aldehydes [Eq. (30)].…”

“…The corresponding silver complex 105a binds to the same ligand and two molecules of methyl isocyanoacetate ( 11a ). [60] Limiting the available methyl isocyanoacetate ( 11a ), or increasing the temperature from –10°C to 25°C, favors a tricoordinate silver structure, similar to 104a , which affords the oxazoline 103 more selectively.…”

Asymmetric Formal [3+2] Cycloaddition Reaction of Isocyanoesters to 2‐Oxobutenoate Esters by a Multifunctional Chiral Silver Catalyst

“…[8] Unfortunately, the expansion of this protocol to an unsaturated carbonyl compound 2 a provided a moderate yield with low levels of stereoselectivity. [9] To address this challenge, and inspired by the asymmetric ferrocenyl-gold(I)/silver(I)-catalyzed aldol reactions of isocyanoacetate and tosylmethyl isocyanides with aldehydes, [10,11] we turned our attention to a Lewis-acid-catalyzed asymmetric version of the cyclization between isocyanoesters and 2-oxobutenoate esters. Although a similar reaction catalyzed by silver acetate has been reported, [12] no enantioselective version is available.…”

Silver‐Catalyzed Isocyanide‐Alkyne Cycloaddition: A General and Practical Method to Oligosubstituted Pyrroles

“…A typical example is the recent pioneering work of Lei and co-workers, who reported the Ag 2 CO 3mediated oxidative cyclization of terminal alkynes with 1,3dicarbonyl compounds or 2-aminopyridines, [15] in which no homocoupling products were observed. [16] On the basis of these precedents and our continued efforts in metalcatalyzed cyclizations, [17] we envisaged that Ag 2 CO 3 might be the right catalyst for the cycloaddition of isocyanides with terminal alkynes. [16] On the basis of these precedents and our continued efforts in metalcatalyzed cyclizations, [17] we envisaged that Ag 2 CO 3 might be the right catalyst for the cycloaddition of isocyanides with terminal alkynes.…”