One-Pot Synthesis of Tertiary α,ω-Diamines via Carbonylative Bis[hydroaminomethylation] of α,ω-Diolefins Using Di(μ-chloro)bis(η4-1,5-cyclooctadine)dirhodium as a Catalyst Precursor

Abstract

Tertiary a,w-diamines are selectively prepared in high yields by the reaction of a,w-diolefins with secondary amines, carbon monoxide and hydrogen in the presence of [Rh(cod)Cl] 2 as a catalyst precursor. This one-pot synthesis proceeds via a hydroformylation-amine condensation-reduction sequence and leads to a mixture of n,n-, n,iso-, and iso,iso-products. One-Pot Synthesis of Tertiary a a, w w-Diamines via Carbonylative Bis[hydroaminomethylation] of a a, w w-Diolefins Using Di(m m-chloro)bis(h h 4 -1,5-cyclooctadiene)dirhodium as a Catalyst Precursor

Catalytic Markovnikov and anti‐Markovnikov Functionalization of Alkenes and Alkynes: Recent Developments and Trends

“…[59] a,w-Diamines with long aliphatic chains separating the two amino functions can also be synthesized by carbonylative bishydroaminomethylation of the corresponding a,w-diole-fins together with suitable amines (Scheme 17). [61] Problems of regioselectivity are circumvented by introducing bulky groups in the vicinity of the double bond. Thus, the two methyl groups of 3,3-dimethylpenta-1,4-diene effect an exclusive formation of the n,n-isomer.…”

Hydroaminomethylation of the Renewable Limonene with Ammonia in an Aqueous Biphasic Solvent System

“…For this transition metal-catalyzed tandem reaction a catalyst based on [Rh(cod)Cl] 2 was employed which showed high activities in reported hydroaminomethylation reactions [33][34][35][36][37][38][39][40]. In Figure 3.…”

“…Our article provides an overview of general amination reactions using terpenes as starting materials, also including a hydroaminomethylation research overview for other amines than ammonia [24]. The so far described hydroaminomethylations of the natural resource limonene were performed with different amine substrates yielding secondary and tertiary amines [25][26][27]. Rhodium/ phosphine complexes showed very high activities for the product formation.…”

Rhodium‐Catalyzed Bis‐Hydroaminomethylation of Linear Aliphatic Alkenes with Piperazine

“…(ii)B ye mployingasubstrate bearing two reactive sites,at wo-fold hydroaminomethylation is conceivable,i nw hich twon ew independent C À N bonds are formed under the same reaction conditions [reactions (II) and( III), Scheme 2].T his can either be accomplishedb ya pplying ad iolefin or ad iamine in combination with the corresponding stoichiometrica mount of amine or olefin, respectively.W er efer to the term "bis-hydroaminomethylation (bis-HAM)"f or these reactions,i n accordance with Eilbracht et al [27] Only af ew examples can be found in which either of the aforementioned conceptsf or the two-fold HAM have been achieved,a nd no generalp rotocol has been developed so far. [19] In particular, bis-hydroaminomethylations applying ad iaminea nd am onoolefin are especially rare.T able 1s ummarizes bis-hydroaminomethylations in which piperazine( 3), the most frequently used diaminec omponent, was applied.…”

“…[25,26] But only in the last two decades,i t became ag eneral tool for the production of various amines (fine chemicals,p harmaceuticals,e tc.) from olefins,p articularly due to the work of Eilbracht, [27][28][29][30][31][32][33] Beller, [23,[34][35][36] and Zhang. [37][38][39][40][41][42] Generally, hydroaminomethylations are,h owever, limited to the aforementioned three auto-tandem catalytic steps and only scattered examples deal with the extensiono ft his sequence.A mong them are combinations of HAM with concurrent esterification of the applied amino acid, [43] formation of the required syngas atmosphere from CO 2 by preliminary reversed water-gas shift (RWGS) reaction [31] andt he access to linear aminesf rom internal alkenes by isomerizing hydroaminomethylation.…”