Anti-Markovnikov Hydroamination of Homoallylic Amines

Abstract

The development of an anti-Markovnikov-selective hydroamination of unactivated alkenes is a significant challenge in organometallic chemistry. Herein, we present the rhodium-catalyzed anti-Markovnikov-selective hydroamination of homoallylic amines. The proximal Lewis basic amine serves to promote reactivity and enforce regioselectivity through the formation of the favored metallacycle, thus over-riding the inherent reactivity of the alkene. The scope of both the amine nucleophiles and homoallylic amines that participate in the reaction is demonstrated.

Iridium-catalyzed Markovnikov hydrosilylation of terminal alkynes achieved by using a trimethylsilyl-protected trihydroxysilane

“…Developing hydrosilylation systems showing excellent tolerance toward them would be of great value. Meanwhile, the pre-existing heteroatoms or functional groups could usually provide inductive effect 51,52 , or coordinate with the metal center [53][54][55][56][57] , both of which might contribute to enhancing the selectivity in hydrofunctionalization reactions. With above considerations, phenyl propargyl ether was selected as the model alkyne substrate to initiate our study ( Table 1).…”

Experimental and Computational Mechanistic Studies of the β‐Diketiminatoiron(II)‐Catalysed Hydroamination of Primary Aminoalkenes

“…Despite major advances in this direction, the development of late d‐block metal hydroamination catalysts for unprotected primary aliphatic amines, arguably the most versatile amines to start an ′′ideal synthesis′′, remains challenging . To date, only few research groups have tackled this difficult issue with catalytic systems that are based on either Rh,, Ir,,– Pt, Au,, Zn, or Cu for mainly the cyclohydroamination of primary amines tethered to unactivated alkenes under mild to harsh conditions. However, these systems are restricted in scope and/or derived from noble metals of limited availability, high price and significant toxicity.…”

First-Row Late Transition Metals for Catalytic Alkene Hydrofunctionalisation: Recent Advances in C-N, C-O and C-P Bond Formation

“…As a general trend, the catalysed N-H and O-H addition reactions across unactivated carbon-carbon double bond afford the Markovnikov adduct while the corresponding P-H addition reactions proceed by an anti -Markovnikov regioselectivity. Only a few reports display the opposite regiochemistry for the appropriate transformation [ 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 ] highlighting the challenges to attain both synthetically valued regioisomers. Another central concern of this domain is the stereochemistry control during the carbon-heteroatom bond formation of the Markovnikov pathway.…”