9 research outputs found
Diastereoselective synthesis of substituted 2-amino-1,3-propanediols from Morita-Baylis-Hillman adducts
We report herein a new diastereoselective approach to substituted 2-amino-1,3-propanediols with anti relative stereochemistry from Morita-Baylis-Hillman (MBH) adducts. These structural moieties have been used as intermediates for the synthesis of several compounds with relevant pharmacological and commercial interest. In this strategy, substituted anti 2-amino-1,3-propanediols were readily prepared via ozonolysis of allylic diols obtained from MBH adducts, followed by a diastereoselective reductive amination of the substituted 2-oxo-1,3-propanediols. To demonstrate the synthetic utility of these aminodiols, they were transformed into substituted oxazolidin-2-ones, which were also used in the indirect determination of the relative stereochemistry of the aminodiols.Descrevemos nesse artigo uma abordagem diastereosseletiva, a partir de adutos de Morita-Baylis-Hillman (MBH), para a preparação de sistemas 2-amino-1,3-propanodióis substituídos com estereoquímica relativa anti. Estas unidades estruturais têm sido utilizadas como intermediárias para a síntese de diversas substâncias de interesse farmacológico e comercial. Nessa estratégia, os anti 2-amino-1,3-propanodióis foram facilmente preparados por ozonólise de dióis alílicos obtidos de adutos de MBH, seguido de uma aminação redutiva diastereosseletiva dos 2-oxo-1,3-propanodióis. Para demonstrar a utilidade desses aminodióis, eles foram transformados em oxazolidin-2-onas substituídas, que também foram utilizadas na determinação indireta da configuração relativa dos aminodióis.285293Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq
Catalytic Enantioselective Synthesis of Allylic Boronates Bearing a Trisubstituted Alkenyl Fluoride and Related Derivatives
The first catalytic method for diastereo- and enantioselective synthesis of allylic boronates bearing a Z-trisubstituted alkenyl fluoride is disclosed. Boryl substitution is performed with either a Z- or E-allyldifluoride and is catalyzed by bisphosphine/Cu complexes, affording products in up to 99 % yield with >98:2 Z/E selectivity and 99:1 enantiomeric ratio. A variety of subsequent modifications are feasible, and notable examples are diastereoselective additions to aldehydes/aldimines to access homoallylic alcohols/amines containing a fluorosubstituted stereogenic quaternary center
Catalytic Enantioselective Synthesis of Amino Skipped Diynes
The Cu-catalyzed synthesis of nonracemic
3-amino skipped diynes
via an enantiodetermining C–C bond formation is described using
StackPhos as ligand. Despite challenging issues of reactivity and
stereoselectivity inherent to these chiral skipped diynes, the reaction
tolerates an extremely broad substrate scope with respect to all components
and provides the title compounds in excellent enantiomeric excess.
The alkyne moieties are demonstrated here to be useful synthetic handles,
and 3-amino skipped diynes are convenient building blocks for enantioselective
synthesis
Controlling Regiochemistry in the Gold-Catalyzed Synthesis of Unsaturated Spiroketals
A novel
gold-catalyzed synthesis of unsaturated spiroketals that
addresses regioselectivity issues commonly reported in metal-catalyzed
spiroketalization of alkynes is reported. The reaction sequence is
regulated by an acetonide protecting group which undergoes extrusion
of acetone to deliver the desired spiroketals in good yields and diastereoselectivities.
The reaction, which is carried out under very mild conditions employing
AuCl as the catalyst, should be widely applicable in the synthesis
of a broad range of spiroketals
Incorporation of Axial Chirality into Phosphino-Imidazoline Ligands for Enantioselective Catalysis
A complementary
strategy for ligand tuning that enables controlling
ligand conformation is described here. The concept is demonstrated
with new ligands that are employed in the catalytic enantioselective
preparation of the highly important C2-aminoalkyl five-membered heterocycle
motif. The alkynylation/cyclization sequence developed here is convergent,
highly modular, and allows for a complementary scope to the heteroarylation
of imines. This new ligand platform should offer new possibilities
for expanding the use of PHIM-type ligands in a large variety of new
transformations