Transition-Metal-Free Borylation of Alkyl Iodides via a Radical Mechanism

Abstract

We describe an operationally simple transition-metal-free borylation of alkyl iodides. This method uses commercially available diboron reagents as the boron source and exhibits excellent functional group compatibility. Furthermore, a diverse range of primary and secondary alkyl iodides could be effectively transformed to the corresponding alkylboronates in excellent yield. Mechanistic investigations suggest that this borylation reaction proceeds through a single-electron transfer mechanism featuring the generation of an alkyl radical intermediate.

Modification of TiO2 Nanoparticles with Organodiboron Molecules Inducing Stable Surface Ti3+ Complex

“…We were particularly interested in the use of organic diboron reagents because of their unique Lewis acidity and reducing ability ( vide supra ). Previous work in the area of synthetic organic chemistry showed that, upon binding to a Lewis basic oxygen atom, these organic diboron species can function as single electron reducing agents, thus allowing for various important transformations (Liu et al., 2019, Mo et al., 2010, Mo et al., 2018, Pietsch et al., 2015, Wang et al., 2016, Zhang and Jiao, 2017). Based on these reasons, we envisioned that, upon the coordination of such diboron compounds with the surface oxygen atom in metal oxide materials, the formation of surface diboron-oxygen Lewis pair may induce single electron transfer from the ipso -O 2c site to the adjacent Ti site.…”

Photoinduced Radical Borylation of Alkyl Bromides Catalyzed by 4‐Phenylpyridine

“…Interestingly, as a most prevalent and readily available alkyl source, alkyl halides have not been utilized in these reactions until very recently. The Studer group reported a metal‐free radical borylation of alkyl iodides under visible‐light irradiation, the Mo group realized a t ‐BuOLi‐promoted radical borylation of alkyl iodides, and the Melchiorre group achieved a photoinduced borylation of benzyl and allyl halides . However, in these reports, more reactive alkyl halides must be employed (Scheme b), and the transition‐metal‐free borylation of unactivated alkyl bromides has not been achieved to date.…”

Organic Borylation Reactions via Radical Mechanism

“…2019 年, 我们课题组报道了无过渡金属参与的、非 光催化的烷基卤化物的自由基硼酯化反应(图 18b) [50] . 该反应的特点为硼源 B 2 pin 2 相对廉价, 对水氧不敏感, 反应条件与实验操作简便易行.…”