An efficient one-pot synthesis of polysubstituted pyrrolizines from N-vinyl-α,β-unsaturated nitrones and activated alkynes through iron­(III)/copper­(II)-cocatalyzed [3 + 2] cycloaddition/[3,3]-rearrangement and sequential N–O bond cleavage was developed. The reaction first underwent [3 + 2] cycloaddition and [3,3]-rearrangement to afford nine-membered N-heterocycles, and then a controlled N–O bond cleavage of nine-membered rings by iron­(III)/copper­(II) cocatalysts delivered pyrrolizine scaffolds. A kinetic resolution of nine-membered ring compounds was achieved for the first time by using copper­(II) acetate combined with a chiral PyBox ligand.

Amides are essentially inert carboxyl derivatives in many types of chemicalt ransformations.I np articular,d eoxygenative CÀCb ond formation of amides to synthetically important amines is al ong-standing challenge for synthetic chemists due to the inertness of the resonance-stabilized amide C = Ob ond. Herein, it is disclosed that by merging electrontransfer-induced activation with 1,2-metalate rearrangement, awide range of aromatic amides react smoothly with arylboron reagents,a ffording as eries of biologically relevant diarylmethylamines as deoxygenative CÀCb ond cross-coupling products.Withits simplicity and versatility,this reaction shows great promise in the synthesis of amines from amides,w hich may open up new avenues in retrosynthetic planning and find widespread use in academia and industry.Scheme 1. Merging electron transfer with 1,2-metalate rearrangement for the deoxygenative functionalization of amides.

A metal-free construction of highly diastereoselective nine-membered heterocycles is described via the cycloaddition and rearrangement of N-vinyl-a,b-unsaturated ketonitrones and isocyanates. Notably, the prepared nine-membered heterocycles afforded 2,3-dihydropyrrolizines under heating conditions. Mechanistic studies showed that the nine-membered rings might undergo decarboxylation, isomerization, aza-Michael addition, and aromatization to afford 2,3-dihydropyrrolizines in a one-pot reaction.

While metal carbene-mediated Si−H insertion reactions have become a powerful strategy to build new C−Si bonds, the utilization of α-aminocarbene intermediates generated from readily available precursors in the Si−H insertion reaction remains a longstanding challenge. Herein, we develop a practical and general strategy to synthesize α-aminosilanes through a deoxygenative cross-coupling of amides and silanes mediated by Sm/SmI 2 . Given the simplicity and versatility, this methodology represents a fascinating example for the effective utilization of inert amides as α-aminocarbene precursors in organic synthesis.

Amides are essentially inert carboxyl derivatives in many types of chemicalt ransformations.I np articular,d eoxygenative CÀCb ond formation of amides to synthetically important amines is al ong-standing challenge for synthetic chemists due to the inertness of the resonance-stabilized amide C = Ob ond. Herein, it is disclosed that by merging electrontransfer-induced activation with 1,2-metalate rearrangement, awide range of aromatic amides react smoothly with arylboron reagents,a ffording as eries of biologically relevant diarylmethylamines as deoxygenative CÀCb ond cross-coupling products.Withits simplicity and versatility,this reaction shows great promise in the synthesis of amines from amides,w hich may open up new avenues in retrosynthetic planning and find widespread use in academia and industry.Scheme 1. Merging electron transfer with 1,2-metalate rearrangement for the deoxygenative functionalization of amides.

This paper sets up a VAR(1) model by collecting the quarterly data on China's macroeconomic and real estate industry. By means of Granger Casualty Test, impulse response function and variance decomposition, the paper studies the impact of macroeconomic variables on real estate variables. The conclusions are as follows: changes in the macroeconomic system have a significant impact on the investment in the real estate development investment and the domestic lending; and the fluctuations of housing price, to some extent, are short of the support of macroeconomic fundamentals and effective demands.

Various A-imino ketones were prepared in good yields through a copper-mediated difunctionalization of alkenylboronic acids with benzotriazolamine in air. Mechanistic studies showed that A-imino ketones formation occurred through an initial copper-mediated coupling reaction to form an enamine, followed by homolysis of the CÀCu bond to produce an A-radical imine, and finally radical oxidation by air. The A-imino ketones were easily converted to various useful scaffolds through further transformations.

A direct deoxygenative silylation of amides with silylboronate reagents is developed in the presence of SmI2/Mg, affording a variety of high value-added α-aminosilane compounds in moderate to excellent yields with good functional group compatibility. The key to the success of this strategy lies in the merging of activation of amides induced by electron transfer with 1,2-metalate migration. The addition of Xantphos ligand can improve the reaction efficiency. The reactions are operationally simple and proceed under mild conditions, the raw materials are easily available and the products are highly valuable.