This Review summarizes the advances in the construction of all-carbon quaternary stereocenters via catalytic enantioselective desymmetrization of prochiral and meso-compounds, highlights the power and potential of this strategy in the total synthesis of natural products and biologically active compounds, and outlines the synthetic opportunities still available.

Catalytic Enantioselective Desymmetrization Reactions to All-Carbon Quaternary Stereocenters.

A Longitudinal Study of Alkaloid Synthesis Reveals Functional Group Interconversions as Bad Actors.

EtOH-catalyzed electrosynthesis of imidazolidine-fused sulfamidates from N-sulfonyl ketimines, N-arylglycines and formaldehyde

Electrocatalytic three-component reactions: synthesis of tellurium-containing oxazolidinone for anticancer agents

The Wacker process, which is widely used to convert monosubstituted alkenes into the corresponding methyl ketones, is thought to proceed through a PdII/Pd0 catalytic cycle involving a β-hydride elimination step. This mechanistic scenario is inapplicable to the synthesis of ketones from the 1,1-disubstituted alkenes. Current approaches based on semi-pinacol rearrangement of PdII intermediates are limited to the ring expansion of highly strained methylene cyclobutane derivatives. Herein, we report a solution to this synthetic challenge by designing a PdII/PdIV catalytic cycle incorporating a 1,2-alkyl/PdIV dyotropic rearrangement as a key step. This reaction, compatible with a broad range of functional groups, is applicable to both linear olefins and methylene cycloalkanes, including macrocycles. Regioselectivity favors the migration of the more substituted carbon, and a strong directing effect of the β-carboxyl group was also observed. Description Elevating Wacker to a higher state Wacker oxidation uses palladium catalysis to produce aldehydes or ketones from olefins and water. The generally accepted mechanism relies on a hydride migration, which is not possible in geminally disubstituted olefins, which lack the requisite hydrogen. Feng et al. report a method to promote carbon migration in this class of substrates by oxidizing a catalyst intermediate to the PdIV state. The resulting pathway converts a wide variety of alkyl and aryl olefins into ketones. —JSY Palladium oxidation promotes a Wacker reaction variant with substrates that require migration of carbon rather than hydrogen.

Oxidative rearrangement of 1,1-disubstituted alkenes to ketones

Abstract The asymmetric Pictet–Spengler reaction (PSR) with aldehydes is well known. However, PSR involving ketones as electrophilic partners is far‐less developed. We report herein the first examples of catalytic enantioselective PSR of tryptamines with α‐ketoamides. A new class of easily accessible prolyl‐urea organocatalysts bearing a single H‐bond donor function catalyzes the title reaction to afford 1,1‐disubstituted tetrahydro‐β‐carbolines in excellent yields and enantioselectivities. The kinetic isotope effect using C2‐deuterium‐labelled tryptamine indicates that the rearomatization of the pentahydro‐β‐carbolinium ion intermediate might be the rate‐ and the enantioselectivity‐determining step.

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/anie.202201788

Catalytic Enantioselective Pictet–Spengler Reaction of α‐Ketoamides Catalyzed by a Single H‐Bond Donor Organocatalyst

Electrochemical Synthesis of Carbamo(dithioperoxo)thioates through the Dehydrogenation Coupling of Thiols and Amines and the Insertion of CS2

2,3-Dihydrobenzofurans are crucial building blocks in the synthesis of natural products and pharmaceutical molecules. However, their asymmetric synthesis has been a long-standing formidable challenge so far. In this work, we developed a highly enantioselective Pd/TY-Phos-catalyzed Heck/Tsuji-Trost reaction of o-bromophenols with various 1,3-dienes, allowing expedient access to chiral substituted 2,3-dihydrobenzofurans. This reaction features excellent regio- and enantiocontrol, high functional group tolerance, and easy scalability. More importantly, the demonstration of this method as a highly valuable tool for the construction of optically pure natural products (R)-tremetone and fomannoxin is highlighted.

Palladium/TY-Phos-Catalyzed Asymmetric Heck/Tsuji-Trost Reaction of o-Bromophenols with 1,3-Dienes.

We report herein an asymmetric Pictet-Spengler reaction of a-ketoesters. In the presence of a catalytic amount of simple alanine-derived squaramide and p-nitrobenzoic acid, reaction of tryptamines with methyl 2-oxoalkanoates affords the corresponding 1-alkyl-1-methoxycarbonyl tetrahydro-β-carbolines (THBCs) in high yields and enantiomeric excesses. A primary kinetic isotope effect (KIE = 4.5) using C2-deteurium labelled tryptamine indicates that rearomatization via deprotonation of the pentahydro-b-carbolinium ion could be the rate and enantioselectivity determining step. A concise enantioselective total synthesis of (+)-alstratine A, a hexacyclic cagelike monoterpene indole alkaloid, featuring this reaction as a key step, is subsequently accomplished. Re-measurement of the natural product's [α]D indicates that natural alstratine A is dextrorotatory rather than levorotatory as it is initially reported in the isolation paper.

Organocatalytic Enantioselective Pictet-Spengler Reaction of α-Ketoesters: Development and Application to the Total Synthesis of (+)-Alstratine A.

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Oxidative rearrangement of 1,1-disubstituted alkenes to ketones

Catalytic Enantioselective Pictet–Spengler Reaction of α‐Ketoamides Catalyzed by a Single H‐Bond Donor Organocatalyst

Electrochemical Synthesis of Carbamo(dithioperoxo)thioates through the Dehydrogenation Coupling of Thiols and Amines and the Insertion of CS2

Palladium/TY-Phos-Catalyzed Asymmetric Heck/Tsuji-Trost Reaction of o-Bromophenols with 1,3-Dienes.

Organocatalytic Enantioselective Pictet-Spengler Reaction of α-Ketoesters: Development and Application to the Total Synthesis of (+)-Alstratine A.