Hydroamination Of Unactivated Alkenes Research Articles

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

This review summarizes the most noteworthy achievements in the field of C–O and C–N bond formation by hydroalkoxylation and hydroamination reactions on unactivated alkenes (including 1,2- and 1,3-dienes) promoted by earth-abundant 3d transition metal catalysts based on manganese, iron, cobalt, nickel, copper and zinc. The relevant literature from 2012 until early 2021 has been covered.

Development of highly efficient platinum catalysts for hydroalkoxylation and hydroamination of unactivated alkenes

Hydrofunctionalization, the direct addition of an X–H (e.g., X=O, N) bond across an alkene, is a desirable strategy to make heterocycles that are important structural components of naturally occurring molecules. Described here is the design and discovery of “donor–acceptor”-type platinum catalysts that are highly effective in both hydroalkoxylation and hydroamination of unactivated alkenes over a broad range of substrates under mild conditions. A number of alkene substitution patterns are accommodated, including tri-substituted, 1,1-disubstituted, (E)-disubstituted, (Z)-disubstituted and even mono-substituted double bonds. Detailed mechanistic investigations suggest a plausible pathway that includes an unexpected dissociation/re-association of the electron-deficient ligand to form an alkene-bound “donor–acceptor”-type intermediate. These mechanistic studies help understand the origins of the high reactivity exhibited by the catalytic system, and provide a foundation for the rational design of chiral catalysts towards asymmetric hydrofunctionalization reactions.

ChemInform Abstract: anti‐Markovnikov Hydroamination of Homoallylic Amines.

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.

Anti-Markovnikov Hydroamination of Homoallylic Amines.

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.

ChemInform Abstract: One‐Pot anti‐Markovnikov Hydroamination of Unactivated Alkenes by Hydrozirconation and Amination.

AbstractThis method tolerates a broad variety of functional groups and can be used for the synthesis of primary and secondary amines.

Gold versus Silver‐Catalyzed Intermolecular Hydroaminations of Alkenes and Dienes

AbstractComparative studies about the hydroamination of unactivated alkenes and dienes catalyzed by either cationic gold(I) triphenyl phosphite complexes or silver salts were performed using sulfonamides, anilines and carbamates as nucleophiles. Gold‐catalyzed reactions generally, need lower loadings than those carried out with silver salts. Simple alkenes react only with sulfonamides and weak aromatic amines such as p‐nitroaniline, whereas for conjugated dienes carbamates can also be used. Carbon‐carbon double bond isomerization is observed only with gold similarly to when triflic acid was used, affording mixtures of regioisomeric products in the same cases. Silver‐catalyzed hydroaminations failed with terminal alkenes, except with styrenes. Conjugate dienes can be hydroaminated either at 85 °C in toluene or at room temperature in dichloromethane. Non‐conjugated 1,4‐ and 1,5‐dienes suffer double hydroamination leading to saturated N‐tosylated heterocyclic amines The catalytic cycle for the silver(I)‐catalyzed hydroamination process has been computationally analyzed, resembling gold(I)‐catalyzed processes, although with some significant differences.

ChemInform Abstract: The Hydroamination of Unactivated Alkenes with Sulfonamides Catalyzed by Phosphomolybdic Acid/SiO2.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

InBr3‐Catalyzed Intermolecular Hydroamination of Unactivated Alkenes.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Gold‐Catalyzed Hydroamination of C—C Multiple Bonds

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Phosphine Gold(I)-Catalyzed Hydroamination of Alkenes under Thermal and Microwave-Assisted Conditions

[reaction: see text] Phosphine gold(I) complexes catalyzed isomerization of terminal alkenes and hydroamination of unactivated alkenes under thermal and microwave-assisted conditions. This is the first example of the use of microwave radiation as a heat source for gold(I)-catalyzed organic reactions.