Oxime‐Derived Iminyl Radicals in Selective Processes of Hydrogen Atom Transfer and Addition to Carbon‐Carbon π‐Bonds

Abstract Oximes represent one of the fundamental organic compound classes with a wide range of synthetic applications. In the last decade O‐substituted oximes were recognized as the synthetically available and versatile precursors of iminyl radicals via one‐electron oxidation or one‐electron reduction employing visible light photoredox catalysts, salts...

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Synthesis of Dibenzosiloles through Electrocatalytic Sila‐Friedel‐Crafts Reaction

Abstract A novel electrocatalyzed method for the preparation of dibenzosiloles was developed through intramolecular C−H/Si−H dehydrogenative coupling strategy starting from biarylhydrosilanes. Both electro‐donating and electro‐withdrawing substitution groups were tolerated for this transformation, and the desired dibenzosilole products could be obtained...

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Double Ligands Enabled Ruthenium Catalyzed ortho‐C–H Arylation of Dialkyl Biarylphosphines: Straight and Economic Synthesis of Highly Steric and Electron‐Rich Aryl‐Substituted Buchwald‐Type Phosphines

A double ligands enabled ruthenium catalyzed C(sp2)‐H arylation of dialkyl phosphines is discribed, which provides a straight access to aryl‐substituted dialkyl phosphine ligands. The combination of 1,3‐diketone and amino acid ligands is essential for this transformation. An important six‐membered cycloruthenium intermediate was successfully isolated...

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peri‐Xanthenoxanthene (PXX): a Versatile Organic Photocatalyst in Organic Synthesis

Abstract Recent years have witnessed a continuous development of photocatalysts to satisfy the growing demand of photophysical and redox properties in photoredox catalysis, with complex structures or alternative strategies devised to access highly reducing or oxidising systems. We report herein the use of peri‐xanthenoxanthene (PXX), a simple and inexpensive...

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Recent Advances in the Synthesis of Spiro‐β‐Lactams and Spiro‐δ‐Lactams

Abstract Spirocyclic molecules are widely recognized for their complex three‐dimensional features and structural rigidity. Among this class of molecules, the spiro‐lactams subclass stands out, being extensively explored due to its bioactivity and utility in a variety of scientific fields such as drug design and organic synthesis. Given the recognition...

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Visible‐Light‐Induced Manganese‐Catalyzed Reactions: Present Approach and Future Prospects

Visible light‐induced reactions have allowed researchers to attain unorthodox bond formation and elusive chemical processes under mild and inherently safe reaction conditions. However, these methods heavily relied on Ru‐ and Ir‐based complexes or metal‐free chromophores. While the heavy transition metal complexes are limited by their high cost, toxicity...

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Asymmetric Allylation Catalyzed by Chiral Phosphoric Acids: Stereoselective Synthesis of Tertiary Alcohols and a Reagent‐Based Switch in Stereopreference

The substrate scope of the asymmetric allylation with zinc organyls catalyzed by 3,3‐bis(2,4,6‐triisopropylphenyl)‐1,1‐binaphthyl‐2,2‐diyl hydrogenphosphate (TRIP) has been extended to non‐cyclic ester organozinc reagents and ketones. Tertiary chiral alcohols are obtained with ee’s up to 94% and two stereogenic centers can be created. Compared to the...

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Solvent‐Dependent Chemoselective and Stereoselective Approach to Synthesis of Spiro‐γ‐Lactams with Potent Anticancer Activity

Chemoselective approaches were developed for derivatizing diastereoselective chromanone spiro‐γ‐lactams through the Michael‐type addition by using amide as a weak nucleophile to construct the spiro‐carbon center under basic conditions. To expand the scope of this post‐Ugi cascade reaction, a new series of oxidized chromone derivatives was synthesized...

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Palladium‐Catalyzed Regioselective and Stereospecific Ring‐Opening Suzuki‐Miyaura Arylative Cross‐Coupling of 2‐Arylazetidines with Arylboronic Acids

Abstract We have developed a palladium‐catalyzed regioselective and enantiospecific ring‐opening Suzuki–Miyaura arylative cross‐coupling of N‐tosyl‐2‐arylazetidines to give enantioenriched 3,3‐diarylpropylamines. This reaction represents an example of transition‐metal‐catalyzed ring‐opening cross‐coupling using azetidines as a non‐classical alkyl electrophile....

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Gold‐Catalyzed Carboamination of Allenes by Tertiary Amines Proceeding with Benzylic Group Migration

Abstract Tertiary amines bearing a benzyl‐type group (CH2Ar) undergo Au(I)‐catalyzed intramolecular addition to allenes. A formal 1,3‐transfer of the CH2Ar group takes place during the cyclization. As demonstrated by both experimental and DFT studies, these unprecedented intramolecular carboaminations involve two consecutive [3,3] rearrangements via...

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