Nickel-Catalyzed Remote C(sp³)–N/O Bond Formation of Alkenes with Unactivated Amines and Alcohols

Abstract

Transition metal-catalyzed remote hydrofunctionalization of alkenes is an efficient method to realize C(sp3)–H functionalization. However, remote hydrofunctionalization of alkenes with unactivated amines and alcohols has not been successfully developed to date. Herein, we report an efficient nickel-catalyzed remote hydroamination and hydroetherification of alkenes with unactivated amines and alcohols, accessing a series of gem-diamine and N,O-acetal derivatives in good to high yields (up to 93%) and exclusive regioselectivities. The mechanistic investigations and DFT computations indicated that the use of 2-iodo-2-methylpropane (tBuI) as both a mild hydride source and radical precursor was essential to afford the remote functionalized products. This research work provides an efficient method to install an amino or alkoxyl group at the C(sp3)–H position that is far from the double bond of alkenes.

Nickel-Catalyzed Hydroamination and Hydroalkoxylation of Enelactams with Unactivated Amines and Alcohols

“…On the basis of the results of the control experiments and the previous reports, 14,17 a possible catalytic cycle for the hydroamination of enelactams is provided (Figure 1). First, homolysis of the C−I bond of tBuI generates a tert-butyl radical and iodine radical, simultaneously.…”

“…Therefore, general and efficient methods for accessing various lactams featuring gem -diamines or N , O -acetals are highly desirable. Recently, our group developed an efficient NiH-catalyzed remote hydroamination and hydroalkoxylation of alkenyl amides with unactivated amines and alcohols . On the basis of our developed strategy for the hydrofunctionalization of alkenes and considering the importance of lactams featuring gem -diamines or N , O -acetals, herein, we report a nickel-catalyzed hydroamination and hydroalkoxylation of enelactams with readily available unactivated amines and alcohols, and a series of γ- , δ-, and ε-lactam derivatives featuring gem -diamine or N , O -acetal were prepared with exclusive regioselectivities (Scheme c).…”

Ligand-Controlled NiH-Catalyzed Regiodivergent and Enantioselective Hydroamination of Alkenyl Amides

“…reported an enantioselective hydroamination of allylic amines and homoallylic amines without migration. However, the migratory α- or β-selective hydroamination and enantioselective migratory β-selective hydroamination have not been reported yet . Our protocol also provided a complementary platform for the synthesis of 1,1-diamines.…”

“…However, the migratory αor β-selective hydroamination and enantioselective migratory β-selective hydroamination have not been reported yet. 18 Our protocol also provided a complementary platform for the synthesis of 1,1-diamines.…”

Rhodium(III)-Catalyzed Remote Hydroamidation of Internal Alkenes Via Chain Walking

“…Hong, Yuan, Zhang, and Yu overcame the obstacle of regioselectivity by applying aminoquinoline, amide, and thioether directing groups under nickel catalysis (Scheme B). − Coordination by these directing groups favors functionalization at a specific carbon via the formation of a stabilized metallacycle.…”