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Allylic amines make up an important class of organiccompounds that have inspired the development of numerous methods fortheir synthesis. One of the most effective transformations involves thecoupling of internal alkynes with appropriate nitrogen-containing electro-philes in the presence of a transition metal catalyst. We have developed amethod that allows transformation of terminal alkynes into allylic aminesthrough a copper-catalyzed reductive cross coupling with α-chloro phthalimides. The method has a broad substrate scope and resultsin the highly selective formation of the E-isomer of the anti-Markovnikov hydroamination product. A preliminary mechanistic studysupports a mechanism that involves the hydrocupration of the alkyne and the formation of a solvent-caged radical pair. 

Abstract Hydroalkylation of alkynes is a powerful method for alkene synthesis. However, regioselectivity has been difficult to achieve in transformations of internal alkynes hindering applications in the synthesis of trisubstituted alkenes. To overcome these limitations, we explored using boryl groups as versatile directing groups that can control the regioselectivity of the hydroalkylation and subsequently be replaced in a cross‐coupling reaction. The result of our exploration is a nickel‐catalyzed hydroalkylation of alkynyl boronamides that provides access to a wide range of trisubstituted alkenes with high regio‐ and diastereoselectivity. The reaction can be accomplished with a variety of coupling partners, including primary and secondary alkyl iodides, α‐bromo esters, α‐chloro phthalimides, and α‐chloro boronic esters. Preliminary studies of the reaction mechanism provide evidence for the hydrometalation mechanism and the formation of alkyl radical intermediates. 

We have developed a convergent method for the synthesis of allylic alcohols that involves a reductive coupling of terminal alkynes with α-chloro boronic esters. The new method affords allylic alcohols with excellent regioselectivity (anti-Markovnikov) and an E/Z ratio greater than 200:1. The reaction can be performed in the presence of a wide range of functional groups and has a substrate scope that complements the stoichiometric alkenylation of α-chloro boronic esters performed using alkenyl lithium and Grignard reagents. The transformation is stereospecific and allows for the robust and highly selective synthesis of chiral allylic alcohols. Our studies support a mechanism that involves hydrocupration of the alkyne and cross-coupling of the alkenyl copper intermediate with α-chloro boronic esters. Experimental evidence excludes a radical mechanism of the cross-coupling step and is consistent with the formation of a boron-ate intermediate and a 1,2-metalate shift. 

Abstract Cycles of dehydration and rehydration could have enabled formation of peptides and RNA in otherwise unfavorable conditions on the early Earth. Development of the first protocells would have hinged upon colocalization of these biopolymers with fatty acid membranes. Using atomic force microscopy, we find that a prebiotic fatty acid (decanoic acid) forms stacks of membranes after dehydration. Using LC‐MS‐MS (liquid chromatography‐tandem mass spectrometry) with isotope internal standards, we measure the rate of formation of serine dipeptides. We find that dipeptides form during dehydration at moderate temperatures (55 °C) at least as fast in the presence of decanoic acid membranes as in the absence of membranes. Our results are consistent with the hypothesis that protocells could have formed within evaporating environments on the early Earth.