6,087 research outputs found
Organocatalytic Lewis base functionalisation of carboxylic acids, esters and anhydrides via C1-ammonium or azolium enolates
This tutorial review highlights the organocatalytic Lewis base functionalisation of carboxylic acids, esters and anhydrides via C1-ammonium/azolium enolates. The generation and synthetic utility of these powerful intermediates is highlighted through their application in various methodologies including aldol-lactonisations, Michael-lactonisations/lactamisations and [2,3]-rearrangements.Publisher PDFPeer reviewe
Strong and Confined Acids Enable a Catalytic Asymmetric Nazarov Cyclization of Simple Divinyl Ketones
We report a catalytic asymmetric Nazarov cyclization of simple, acylic, alkyl-substituted divinyl ketones using our recently disclosed strong and confined imidodiphosphorimidate Brønsted acids. The corresponding monocyclic cyclopentenones are formed in good yields and excellent regio-, diastereo-, and enantioselectivities. Further, the chemical utility of the obtained enantiopure cyclopentenones is demonstrated
Phosphoramidite Gold(I)-Catalyzed Diastereo- and Enantioselective Synthesis of 3,4-Substituted Pyrrolidines
In this article the utility of phosphoramidite ligands in enantioselective AuI catalysis was explored in the development of highly diastereo- and enantioselective AuI-catalyzed cycloadditions of allenenes. A Au^I-catalyzed synthesis of 3,4-disubstituted pyrrolidines and γ-lactams is described. This reaction proceeds through the enantioselective AuI-catalyzed cyclization of allenenes to form a carbocationic intermediate that is trapped by an exogenous nucleophile, resulting in the highly diastereoselective construction of three contiguous stereogenic centers. A computational study (DFT) was also performed to gain some insight into the underlying mechanisms of these cycloadditions. The utility of this new methodology was demonstrated through the formal synthesis of (−)-isocynometrine
Versuche zur asymmetrischen Redox-Disproportionierung von meso-Peroxiden. Neue Chrom(III)-und Organokatalysatoren für die asymmetrische Hetero-Diels-Alder Reaktion
Highly Diastereo- and Enantioselective Allylboration of Aldehydes using alpha-Substituted Allyl/Crotyl Pinacol Boronic Esters via in Situ Generated Borinic Esters
A Dynamic Kinetic Asymmetric Heck Reaction for the Simultaneous Generation of Central and Axial Chirality
A highly diastereo- and enantioselective, scalable Pd-catalyzed dynamic kinetic asymmetric Heck reaction of heterobiaryl sulfonates with electron-rich olefins is described. The coupling of 2,3-dihydrofuran or N-boc protected 2,3-dihydropyrrole with a variety of quinoline, quinazoline, phthalazine, and picoline derivatives takes place with simultaneous installation of central and axial chirality, reaching excellent diastereo- and enantiomeric excesses when in situ formed [Pd0/DM-BINAP] was used as the catalyst, with loadings reduced down to 2 mol % in large scale reactions. The coupling of acyclic, electron-rich alkenes can also be performed using a [Pd0/Josiphos ligand] to obtain axially chiral heterobiaryl α-substituted alkenes in high yields and enantioselectivities. Products from Boc-protected 2,3-dihydropyrrole can be easily transformed into N,N ligands or appealing axially chiral, bifunctional proline-type organocatalysts. Computational studies suggest that a β-hydride elimination is the stereocontrolling step, in agreement with the observed stereochemical outcome of the reaction.Ministerio de Ciencia e Innovación (Grants CTQ2016-76908-C2-1-P; CTQ2016-76908-C2-2-P; CTQ2016-78083-P; RYC-2013-12585)European Commission (FEDER Programme)Junta de AndalucÃa (Grant 2012/FQM 10787)Universidad de Sevilla (Grant No. 1800511201)European Union - Marie SkÅ‚odowska-Curie (COFUND—Grant Agreement nº 291780
Relevance of cis- and trans-dichloride Ru intermediates in Grubbs-II olefin metathesis catalysis (H(2)IMesCl(2)Ru=CHR)
Using density functional theory with the B3LYP and M06 functionals, we show conclusively that the (H2IMes)(Cl)2Ru olefin metathesis mechanism is bottom-bound with the chlorides remaining trans throughout the reaction, thus attempts to effect diastereo- and enantioselectivity should focus on manipulations that maintain the trans-dichloro Ru geometry
Asymmetrische organokatalytische Transferhydrierung von zyklischen Enonen,Asymmetrische Iridium-katalysierte Hydrierung von (Aza-) Baylis-Hillman Addukten und Synthese des cis-Takemoto-Katalysators
Dynamic Kinetic Resolution of Hetero biaryl Ketones by Zinc- Catalyzed Asymmetr ic Hydrosil ylation
Adiastereo-
and
highly
enantioselective
dynamic
kinetic
resolution
(DKR)
of configurationally
labile
hetero-
biaryl
ketones
is described.
The
DKR
proceeds
by zinc-
catalyze
dhydrosilylation
of the carbonyl
group
,thus leading
to
secondary
alcohols
bearing
axial
and
central
chirality
.The
strategy
relies
on the labilization
of the stereogenic
axis
that
takes
place
thanks
to aLewis
acid–base
interaction
between
anitrogen
atom
in the heterocycle
and
the ketone
carbonyl
group
.The synthetic
utility
of the methodology
is demonstrated
through
stereospecific
transformations
into either
N,N-ligands
or appealing
axially
chiral,
bifunctional
thiourea
organocata-
lysts.Ministerio de Ciencia e Innovación (Grants CTQ2016-76908-C2-1-P, CTQ2016-76908-C2-2-P, contract RYC-2013-12585)European FEDER FundsJunta de AndalucÃa (Grant 2012/FQM 10787)European Union - Marie SkÅ‚odowska-Curie (COFUND—Grant Agreement n 8 8 291780
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