Abstract Enantiopure vicinal amino alcohols and derivatives are essential structural motifs in natural products pharmaceutically active molecules, serve as main chiral sources asymmetric synthesis. Currently known catalytic protocols for this class of compounds still rare often suffer from limited scope substrates, relatively low regio- or stereoselectivities, thus prompting the development more effective methodologies. Herein we report a dual strategy convergent enantioselective synthesis...

This study reports the catalytic deracemization of ketones bearing stereocenters in α-position a single reaction via deprotonation, followed by enantioselective protonation. The principle microscopic reversibility, which has previously rendered this strategy elusive, is overcome photoredox deprotonation through electron transfer and subsequent hydrogen atom (HAT). Specifically, irradiation racemic pyridylketones presence photocatalyst tertiary amine provides nonracemic carbonyl compounds...

A transformation of fluxional into configurationally stable axially chiral N-arylpyrroles was achieved with a highly atroposelective electrophilic aromatic substitution catalyzed by chiral-at-metal rhodium Lewis acid. Specifically, were alkylated N-acryloyl-1H-pyrazole electrophiles in up to 93 % yield and >99.5 ee, follow-up conversions reveal the synthetic utility this new method. DFT calculations elucidate origins observed excellent atroposelectivity.

Abstract The conversion of C‒H bonds to C‒N offers a sustainable and economical strategy for the synthesis nitrogen-containing compounds. However, challenges regarding control regio- stereoselectivity currently limit broad applicability intermolecular C( sp 3 )‒H amination reactions. We address these restrictions by directed nitrene-mediated insertion using metal-coordinating functional group. report highly stereocontrolled, iron-catalysed direct α-amination abundant carboxylic acid...

ConspectusAsymmetric transition metal catalysis is an indispensable tool used both in academia and industry for forging chiral molecules enantioselective fashion. Its advancement relies large part on the design discovery of new catalysts. In contrast to conventional endeavors generating catalysts from carefully tailored ligands, development containing solely achiral ligands (chiral-at-metal catalysts) has been neglected. This Account presents our recent work synthesis catalytic applications...

Radical measures: A radical coupling reaction, which is proposed to proceed through in situ chlorination of a hydroxy group by Me3SiCl, used form quaternary carbon centers with amino groups α position. The reaction can be scaled up and an efficient six-step total synthesis (±)-9,10-diepi-stemoamide (see scheme, Cp=cyclopentadienyl, EWG=electron-withdrawing group). As service our authors readers, this journal provides supporting information supplied the authors. Such materials are peer...

Abstract 3‐(2‐Formylphenyl)‐1‐pyrazol‐1‐yl‐propenones undergo an asymmetric photorearrangement to benzo[ d ]cyclopropa[ b ]pyranones with up >99 % ee , which is catalyzed by a bis‐cyclometalated rhodium catalyst in the presence of visible light. Mechanistic experiments and DFT calculations support mechanism photoexcited catalyst/substrate complex triggers intramolecular hydrogen‐atom transfer followed highly stereocontrolled hetero‐Diels–Alder reaction. In this reaction scheme, fulfills...

Abstract A transformation of fluxional into configurationally stable axially chiral N‐arylpyrroles was achieved with a highly atroposelective electrophilic aromatic substitution catalyzed by chiral‐at‐metal rhodium Lewis acid. Specifically, were alkylated N‐acryloyl‐1 H ‐pyrazole electrophiles in up to 93 % yield and >99.5 ee , follow‐up conversions reveal the synthetic utility this new method. DFT calculations elucidate origins observed excellent atroposelectivity.

A cyclometalated ruthenium complex with exclusively metal-centered chirality catalyzes the conversion of diazoketones to chiral flavanones up 99% yield and 96% ee. competing oxygen attack pathway involving formation [1,2]-shift (Stevens rearrangement) an oxonium ylide intermediate was successfully suppressed in favor a catalytic enantioselective ring-closing C(sp3)–H carbene insertion. Density functional theory calculations provide rationale for observed C–H insertion over undesirable C–O...

The synthesis of non-racemic 5-membered cyclic carbonates from abundant alcohols is reported. Conversion the alcohol into an azanyl carbonate followed by a chiral-at-ruthenium catalyzed cyclization to provide chiral in yields up 95 % and with 99 ee. This new synthetic method proposed proceed through nitrene-mediated intramolecular C(sp3 )-H oxygenation which includes unusual 1,7-hydrogen atom transfer within ruthenium nitrene intermediate. applicable mono-, di- trisubstituted alkylene carbonates.

Comprehensive Summary Enantioselective or enantioconvergent iron‐catalyzed ring‐closing C(sp 3 )‐H aminations of N ‐aroyloxyurea through intermediate iron nitrene species provide chiral 2‐imidazolidinones in up to 99% yield and with 95% ee (40 examples). This is a rare example which sustainable catalysis combined amination asymmetric catalysis. Chiral are prevalent structural motifs bioactive molecules can also be hydrolyzed valuable vicinal diamines single step.

The asymmetric total synthesis of (-)-14,15-dihydrosecurinine and the formal (-)-securinine were accomplished starting from an easily available malimide. A concise SmI2-mediated radical coupling strategy has been developed to construct bridged α-hydroxy 6-azabicyclo[3.2.1]octanone in four steps with high diastereoselectivity.

Eine radikalische Kupplung, die vermutlich über eine In-situ-Chlorierung einer Hydroxygruppe mit Me3SiCl verläuft, wird für den Aufbau quartärer Kohlenstoffzentren Aminogruppen in α-Position verwendet. Die Reaktion wurde sechsstufigen Totalsynthese von (±)-9,10-Diepistemoamid verwendet (siehe Schema, Cp=Cyclopentadienyl, EWG=elektronenziehende Gruppe). As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer...

Abstract 3‐(2‐Formylphenyl)‐1‐pyrazol‐1‐yl‐propenones undergo an asymmetric photorearrangement to benzo[ d ]cyclopropa[ b ]pyranones with up >99 % ee , which is catalyzed by a bis‐cyclometalated rhodium catalyst in the presence of visible light. Mechanistic experiments and DFT calculations support mechanism photoexcited catalyst/substrate complex triggers intramolecular hydrogen‐atom transfer followed highly stereocontrolled hetero‐Diels–Alder reaction. In this reaction scheme, fulfills...

Abstract N ‐Boc‐protected α‐amino acids are synthesized in two steps from linear or branched carboxylic acid feedstocks. In the first step, is coupled with tert ‐butyl aminocarbonate (BocNHOH) to generate azanyl ester (acyloxycarbamate) RCO 2 NHBoc. second this undergoes a stereocontrolled iron‐catalyzed 1,3‐nitrogen migration non‐racemic acid. This straightforward protocol applicable catalytic asymmetric synthesis of α‐monosubstituted aryl, alkenyl, and alkyl side chains. Furthermore,...

Abstract The synthesis of non‐racemic 5‐membered cyclic carbonates from abundant alcohols is reported. Conversion the alcohol into an azanyl carbonate followed by a chiral‐at‐ruthenium catalyzed cyclization to provide chiral in yields up 95 % and with 99 ee . This new synthetic method proposed proceed through nitrene‐mediated intramolecular C(sp 3 )−H oxygenation which includes unusual 1,7‐hydrogen atom transfer within ruthenium nitrene intermediate. applicable mono‐, di‐ trisubstituted...

Abstract The novel method uses the TiCl 2 (Cp) /Mg/TmsCl catalytic reduction system.