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A transition metal‐free Se‐catalyzed C−H amination protocol for α’‐amination of enol derivatives has been developed. This reaction can be used to functionalize a wide variety of oxygen‐ and halogen‐substituted alkenes spanning a vast range of nucleophilicities, giving α’‐aminated enol derivatives with high regioselectivity. Amination ofE/Zmixtures of alkenes proceeds stereoconvergently to give the (Z)‐enol derivatives exclusively. Mechanistic studies revealed that the relative reactivity and α’‐regioselectivity of these transformations is determined by substantial resonance donation to the heteroatom‐bound carbon in the transition state. These products participate in traditional reactions of enol derivatives, allowing for efficient functionalization of both α‐ and α’‐positions from a single enol derivative with high diastereocontrol.

 

Post‐polymerization modification (PPM) via direct C−H functionalization is a powerful synthetic strategy to convert polymer feed‐stocks into value‐added products. We found that a metal‐free, Se‐catalyzed allylic C−H amination provided an efficient method for PPM of polynorbornenes (PNBs) produced via ring‐opening metathesis polymerization. Inherent to the mechanism of the allylic amination, PPM on PNBs preserved the alkene functional groups along the polymer backbone, while also avoiding transposition of the double bonds. Amination using a series of aryl sulfonamides led to good control over the degree of functionalization, access to a range of functionalities, and tunable thermal properties from the resulting polymers.

 

Vinylsilanes and vinylboronates are common building blocks for organic synthesis, but direct functionalization of these species without the participation of either the C=C or C−Si/B bonds is rare. Herein, we report a metal‐free allylic C−H amination reaction of these vinylmetalloid species that installs a new C−N bond without competing transmetallation or alkene addition. In this transformation, the silicon or boron substituent inverts the usual regioselectivity, directing amination to the site distal to that group. Subsequent cross‐coupling or demetallation allows access to complementary regioisomeric products. Density Functional Theory computations revealed that the observed regioselectivity is due to a subtle combination of electronic and counterintuitive steric factors that favor initial attack of selenium at the silicon‐bearing carbon atom.

 

We report a selenium-catalyzed diamination of dienes using sulfamates as a convenient nitrogen source. This reaction proceeds regioselectively for 1,2-addition at the less substituted alkene, without the need for a tethered diamine. We also report the first diamination of dienyl phosphates and tosylates, affording synthetically useful α,β-diaminoketone derivatives with high syn diastereoselectivity. Density functional theory calculations support a mechanism proceeding via [4+2] cycloaddition of the diene with a selenium bis(imide), followed by ring-opening aminolysis and [2,3]-sigmatropic rearrangement. 

We report a diastereoconvergent synthesis of anti -1,2-amino alcohols bearing N-containing quaternary stereocenters using an intermolecular direct C–H amination of homoallylic alcohol derivatives catalyzed by a phosphine selenide. Destruction of the allylic stereocenter during the selenium-catalyzed process allows selective formation of a single diastereomer of the product starting from any diastereomeric mixture of the starting homoallylic alcohol derivatives, eliminating the need for the often-challenging diastereoselective preparation of starting materials. Mechanistic studies show that the diastereoselectivity is controlled by a stereoelectronic effect (inside alkoxy effect) on the transition state of the final [2,3]-sigmatropic rearrangement, leading to the observed anti selectivity. The power of this protocol is further demonstrated on an extension to the synthesis of syn -1,4-amino alcohols from allylic alcohol derivatives, constituting a rare example of 1,4-stereoinduction.