172478-10-3Relevant articles and documents
Catalytic asymmetric aldol-type reaction of zinc enolate equivalent of amides
Haraguchi, Ryosuke,Matsubara, Seijiro
supporting information, p. 3378 - 3380 (2013/07/26)
Treatment of phenyl isocyanate with bis(iodozincio)methane gave a zinciomethylenated product, which acts as an amide-enoate equivalent. It did not react with an aldehyde efficiently, but gave the corresponding adduct in good yield in the presence of an aminoalcohol. Use of a catalytic amount of chiral aminoalcohol led the process to the catalytic asymmetric Aldol-type reaction.
Reactions of amines and hydrazides derived from L-proline with dialkyl dicyanofumarates
Mloston, Grzegorz,Pieczonka, Adam M.,Wroblewska, Aneta,Linden, Anthony,Heimgartner, Heinz
, p. 343 - 356 (2013/08/15)
The reaction of prolinamine derivatives (8a,b) and dialkyl dicyanofumarates (1) in dichloromethane at room temperature leads to the optically active enamines (10). Whereas products (10) in the case of 1-benzyl prolinamine (8a) are stable compounds, the corresponding enamines obtained from the non-protected prolinamine (8b) smoothly undergo a cyclocondensation at room temperature to give perhydropyrrolo[1,2-a]pyrazine derivatives (11). The molecular structure of 11a was established by X-Ray crystallography. In analogy to 8a, 1-benzyl prolinehydrazide (9a) and 1b in dichloromethane react to yield the enehydrazine (12b). On the other hand, the reaction of 9a and 1 in methanol at room temperature leads to the corresponding dialkyl 3-amino-1H-pyrazole- 4,5-dicarboxylates (13) and methyl 1-benzylprolinate (14b) Via a stepwise mechanism. The analogous reaction was observed between a 3-oxidoimidazole-4- carbohydrazide (15) and 1b.
Studies on the synthesis and some reactions of (S)-proline hydrazides
Mloston, Grzegorz,Pieczonka, Adam M.,Wroblewska, Aneta,Linden, Anthony,Heimgartner, Heinz
experimental part, p. 795 - 801 (2012/09/07)
A convenient synthesis of (S)-proline hydrazide 2a via the reaction of ethyl (S)-N-benzylprolinate with hydrazine hydrate and subsequent deprotection of (S)-N-benzyl proline hydrazide 5 is described. The latter, in methanolic solution, reacted with aromatic aldehydes as well as with cycloaliphatic ketones at room temperature to give the corresponding hydrazones of type 7 in good yields. The structure of the product with furan-2-carbaldehyde 7b, proving the (E)-configuration of the hydrazone, was established by X-ray crystallography. In the case of the unprotected (S)-proline hydrazide 2a, the analogous reaction with aromatic aldehydes led either to the expected hydrazones 7 or the 1H-pyrrolo[1,2-c]imidazol-1-one derivatives 8, depending on the reaction conditions. The latter were formed via a secondary cyclocondensation of the initially formed 7 with a second molecule of the aldehyde. Whereas the reaction of (S)-N-benzyl proline hydrazide 5 with butyl isocyanate and isothiocyanate gave the corresponding semicarbazide and thiosemicarbazide, respectively, of type 9, the unprotected (S)-proline hydrazide 2a yielded the 1:2 adducts 10. Thiosemicarbazide 9b underwent cyclization reactions under basic (NaOH) and acidic (H2SO4) conditions to yield (S)-prolinyl- substituted 1,2,4-triazole-3-thione 11 and 1,3,4-thiadiazole-2-amine 12, respectively.
One-carbon ring expansion of azetidines via ammonium ylide [1,2]-shifts: A simple route to substituted pyrrolidines
Bott, Tina M.,Vanecko, John A.,West
supporting information; scheme or table, p. 2832 - 2836 (2009/08/15)
Simple N-substituted azetidines were heated with diazocarbonyl compounds in the presence of catalytic Cu(acac)2 to furnish substituted pyrrolidines via Stevens [1,2]-shift. In all but two examples, complete selectivity was seen for ring expansion rather than migration of the other exocyclic group on the azetidinium nitrogen. The two exceptions, observed with ylides substituted with two carbonyl groups and lacking a stabilizing group at the 2-position of the azetidine, underwent exocyclic benzyl migration in preference to ring expansion.
Intramolecular Nucleophilic Substitution on Nitrogen A New Heterocyclic Synthesis
Sheradsky, Tuvia,Yusupova, Larissa
, p. 7701 - 7704 (2007/10/02)
A series of 5-(diphenylphosphinyloxyamino)valeric acid esters has been prepared.Their treatment with appropriate bases led to cyclization to proline derivatives.The reaction constitutes the first reported case of intramolecular nucleophilic substitution o
LARGE SCALE PREPARATION OF VERSATILE CHIRAL AUXILIARIES DERIVED FROM (S)-PROLINE
Enders, Dieter,Kipphardt, Helmut,Gerdes, Peter,Brena-Valle, Leonardo J.,Bhushan, Vidya
, p. 691 - 704 (2007/10/02)
The synthesis of a variety of enantiomerically pure chiral auxiliaries based on (S)-proline and bearing sterically demanding side chains at the pyrrolidine moiety, such as the secondary amines (S)-3,5 and 7 and the hydrazines (S)-6, is described on a molar scale.As key step, the Grignard or RLi addition to the N-benzylated proline ester (S)-1 is used.