Catalytic Formal Hydroamination of Allylic Alcohols Using Manganese PNP‐Pincer Complexes

Abstract

Several manganese-PNP pincer catalysts for the formal hydroamination of allylic alcohols are presented. The resulting γ-amino alcohols are selectively obtained in high yields applying Mn-1 in a tandem process under mild conditions.

Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

“…In early 2021, Beller reported the (PNP)Mn( i )-complex Mn31 -catalyzed anti-Markovnikov hydroamination of allyl alcohols to get γ-amino alcohols (Table 22, entry 1). 339 This reaction was performed in cyclohexane solution in the presence of NaHBEt 3 and K 2 CO 3 as the catalyst activator and base, respectively.…”

Earth-Abundant 3d Transition Metal Catalysts for Hydroalkoxylation and Hydroamination of Unactivated Alkenes

“…Despite the interesting features of being of low toxicity and eco-friendly, manganese remains unexploited for the development of catalytic hydroamination and hydroalkoxylation methodologies of unactivated alkenes [40]. To our knowledge, there is only one report of manganese-catalyzed hydroamination of unactivated alkenes [41,42]. This year, the group of Qu and Zhang reported an elegant visible-light-induced manganese-promoted N-F bond activation strategy to generate amidyl radicals from N-fluorinated sulfonamides (Figure 1).…”

Manganese-Catalyzed Anti-Markovnikov Hydroamination of Allyl Alcohols via Hydrogen-Borrowing Catalysis

“…Recently, Xing and Wang groups independently reported asymmetric hydroamination of aryl vinyl alcohols utilizing ruthenium catalysts. While preparing this article, Beller and coworkers reported alkyl phosphine-derived manganese complex-catalyzed formal hydroamination of allyl alcohols using pyrophoric sodium triethylborohydride as the catalyst activator . Although the developed methods are promising, most of them used noble metals as catalysts and external additives as catalyst activators and offered limited scope.…”

“…While preparing this article, Beller and coworkers reported alkyl phosphine-derived manganese complex-catalyzed formal hydroamination of allyl alcohols using pyrophoric sodium triethylborohydride as the catalyst activator. 16 Although the developed methods are promising, most of them used noble metals as catalysts and external additives as catalyst activators and offered limited scope. On the other hand, the modern era of organometallic synthesis demands the development of catalysts based on the Earth's abundant transition metals due to easy accessibility, low cost, and less toxicity.…”