Recent developments in alkene hydro-functionalisation promoted by homogeneous catalysts based on earth abundant elements: formation of C–N, C–O and C–P bond

Abstract

This Perspective article provides an overview of the recent advancements in the field of intra- and inter-molecular C-N, C-O and C-P bond formation by hydroamination, hydroalkoxylation, hydrophosphination, hydrophosphonylation or hydrophosphinylation of unactivated alkenes, including allenes, 1,3-dienes and strained alkenes, promoted by (chiral) homogeneous catalysts based on earth abundant elements of the s and p blocks, the first row transition metals and the rare-earth metals. The relevant literature from 2009 until late 2014 has been covered.

Asymmetric Assisted Tandem Catalysis: Hydroamination followed by Asymmetric Friedel–Crafts Reaction from a Single Chiral N,N,N′,N′‐Tetradentate Pyridylmethylamine‐Based Ligand

“…We speculate that the unexpected difference in reactivity between anilines 5 a and 5 b and tosylaniline derivatives 5 c and 5 d might arise from distinct mechanisms. Most rare‐earth metal catalyzed hydroamination reactions, which are usually performed without a protecting group on the amine, tend to proceed by syn ‐migratory insertion of a RE−N bond across the carbon–carbon double or triple bond . However, in this case, the geometry constraint of the 5‐ endo ‐ dig cyclization required for indole‐ring formation might prevent such a pathway and implicate an alternative mechanism involving anti ‐nucleophilic attack onto the coordinated alkyne (Scheme ).…”

Markovnikov-Selective Addition of Fluorous Solvents to Unactivated Olefins Using a Co Catalyst

“…Based on the consideration, we initiated the optimization of the reaction conditions. As we expected, when 4-allyl-1,2dimethoxybenzene (2a) was subjected to a catalytic amount of catalyst 1 in TFE in the presence of N-fluoro-2,4,6-trimethylpyridinium tetrafluoroborate (Me 3 NFPY·BF 4 ) and 1,1,3,3-tetramethyldisiloxane [(Me 2 SiH) 2 O] under argon, desired product 3a was obtained in 81% yield without anti-Markovnikov adducts ( Table 1, entry 4). In the absence of catalyst 1, N-fluoro-2,4,6-trimethylpyridinium salt, or (Me 2 SiH) 2 O, no reaction took place (entries 1-3).…”

“…NFPY·BF 4 , and (Me 2 SiH)2 O. This reaction condition was found to activate olefins, which enabled them to be attacked by TFE and HFIP, both of which are electronically weak nucleophiles.…”

“…Many research groups have investigated catalytic versions of this reaction to date. [1][2][3] In 2013, we also reported a unique Markovnikov-selective hydroalkoxylation of unactivated olefins with a cobalt (Co) complex, silane, and N-fluoropyridinium salt (Chart 1). This reaction condition enabled unactivated olefins to connect with a wide range of alcoholic solvents, including methanol, ethanol, i-propanol, and t-butanol.…”

Alkene Hydroamination via Earth‐Abundant Transition Metal (Iron, Cobalt, Copper and Zinc) Catalysis: A Mechanistic Overview

“…The relevant literature has been covered from 2012 until early 2019. For early developments, the reader should refer to previously reported reviews . Achievements in the direct addition of electronically biased amines (such as as sulfonamides, carbamates or amides) on unactivated alkenes are beyond the scope of this review as such C−N bond formation reactions are today more appropriately called hydroamidation reactions …”