A ruthenium(II)-catalyzed regioselective direct diamidation of 3-carbonylindoles at the C4- and C5- position using various dioxazolones is described. This novel protocol allows for the effective installation of two amide groups...

We report the isomerisation of α,β-unsaturated diesters to thermodynamically less favourable β,γ-unsaturated carbonyl compounds in the absence of strongly basic anhydrous or photochemical conditions.

Here, we report a highly chemo‐, diastereo‐, and enantioselective allyl‐allyl coupling between branched allyl alcohols and α‐silyl‐substituted allylboronate esters, catalyzed by a chiral iridium complex. The α‐silyl‐substituted allylboronate esters can be chemoselectively coupled with allyl electrophiles, affording a diverse set of enantioenriched (E)‐1‐boryl‐substituted 1,5‐dienes in good yields, with excellent stereoselectivity. By permuting the chiral iridium catalysts and the substrates, we efficiently and selectively obtained all four stereoisomers bearing two consecutive chiral centers. Mechanistic studies via density functional theory calculations revealed the origins of the diastereo‐ and chemoselectivities, indicating the pivotal roles of the steric interaction, the β‐silicon effect, and a rapid desilylation process. Additional synthetic modifications for preparing a variety of enantioenriched compounds containing contiguous chiral centers are also included.

We report a copper‐catalyzed, regioselective, and stereospecific alkylation of unbiased internal allylic carbonates with functionalized alkyl and aryl Grignard reagents. The reactions exhibit high stereospecificity and regioselectivity for either SN2 or SN2′ products under two sets of copper‐catalyzed conditions, which enables the preparation of a broad range of products with E‐alkene selectivity. Density functional theory calculations reveal the origins of the regioselectivity based on the different behaviors of homo‐ and heterocuprates.