Rhodium catalyzed one-step hydroamidation of cyclopentadiene and dicyclopentadiene

Behr, Arno; Levikov, Denys; Nürenberg, Edward

doi:10.1039/c5cy00168d

Cited by 18 publications

(12 citation statements)

References 24 publications

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“…Behr et al already showed the possibility to reduce the dimerization process by the use of tertiary amines as additives, 57 which have a high coordination ability to the metal center 62 as well as to the C-C double bond. Behr et al already showed the possibility to reduce the dimerization process by the use of tertiary amines as additives, 57 which have a high coordination ability to the metal center 62 as well as to the C-C double bond.…”

Section: Resultsmentioning

confidence: 99%

“…[35][36][37][38][39][40][41][42] In contrast just a few investigations with dienes as starting materials for the HAM can be found in the literature, among them the rhodium-catalyzed formation of diamines from a,u-diolens using [Rh(cod)Cl] 2 , 43 conversion of limonene with various amines 44 and reaction of isoprene in an aqueous two-phase system. 57 Therefore, the initial step of the HAM, e.g. 46 Till now only a few technical applications for Cpd are known.…”

Section: Introductionmentioning

confidence: 99%

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Rhodium-catalyzed hydroaminomethylation of cyclopentadiene

2015

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A one-step rhodium catalyzed direct route from cyclopentadiene (Cpd) to saturated C 6 -amines is presented via hydroaminomethylation (HAM). The homogeneous catalyst of Rh(II) octanoate dimer without additional phosphorus ligands was established giving a 77% yield of the monoamine species of Cpd with pyrrolidine within 4 hours. The unwanted reaction of Cpd, the dimerization to dicyclopentadiene (Dcpd), could be suppressed by careful adjustment of the CO : H 2 ratio in the synthesis gas and the choice of solvent, both giving the possibility to steer the reaction to selectively produce amines of either Cpd or Dcpd. Furthermore, other investigated cyclic and non-cyclic aliphatic amine substrates showed excellent selectivity up to 100% for the formation of the HAM-products. CH 3 ); 2.80 (m, 2H, 2CH); 2.21-2.24 (m, 1H, CH); 2.16 (d, 3 J ( 1 H-1 H) ¼ 8 Hz, 2H, CH 2 ), 1.96-2.00 (m, 1H, CH); 1.88-1.92 (m, 2H, 2CH); 1.80 (m, 2H, 2CH); 1.65-1.71 (m, 4H, 2CH 2 ); 1.78-1.82 (m, 2H, 2CH) 1.43-1.53 (m, 4H, 2CH 2 ); 1.10-1.15 (m, 2H, 2CH). 13 C( 1 H) (125.77 MHz, CDCl 3 , TMS) d 13 C [ppm]: 175.95 (s, 1C); 60668 | RSC Adv., 2015, 5, 60667-60673 This journal is Scheme 1 Product range in the hydroaminomethylation of Cpd 1 with pyrrolidine.This journal is

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Rhodium-catalyzed hydroaminomethylation of cyclopentadiene

2015

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“…The effect of competing dimerization is demonstrated by the aminocarbonylation of cyclopentadiene developed in our laboratories . The desired amides of cyclopentadiene were formed only in small amounts under rhodium catalysis with pyrrolidine as the amine component.…”

Section: C5 Moleculesmentioning

confidence: 99%

“…The effect of competing dimerization is demonstrated by the aminocarbonylation of cyclopentadiene developed in our laboratories. [87] The desired amides of cyclopentadiene were formed only in small amounts under rhodium catalysis with pyrrolidine as the amine component. Monosubstituted amides of dicyclopentadiene were the main products formed by in situ dimerization of cyclopentadiene followed by aminocarbonylation ( Figure 39).…”

Section: Carbonylationmentioning

confidence: 99%

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

et al. 2018

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For many years, the efficient use of resources has been a major and permanent challenge for the chemical industry. The implementation of alternative resources such as renewables and carbon dioxide has been a subject of considerable discussion, but also the more efficient use of long known bulk chemicals is of great interest. Among them, 1,3‐dienes such as 1,3‐butadiene from the C4 cut of the naphtha cracker as well as isoprene, piperylene and cyclopentadiene from the corresponding C5 section are important substrates. These dienes are presently employed in various markets, with the greatest importance being in the production of polymers and copolymers. However, homogeneous transition metal catalysis has proven to be a versatile tool to functionalize these important 1,3‐dienes to low molecular weight fine chemicals by introducing, for example, nitrogen, oxygen or silicon. Hence, an upgraded use of the corresponding products as agrochemicals, pharmaceuticals, fragrances or special detergents is close at hand. The main approaches in the topic of homogeneous functionalization reactions of the industrially relevant 1,3‐dienes will be summarized and discussed within the present article. Besides that, novel applications including renewable 1,3‐dienes, for example β‐myrcene and β‐farnesene, as well as the application of CO2 in telomerization, will be critically discussed.

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“…This behavior is simply explained by the stronger basicity of aliphatic amines:F or example,a lanine ester (pK b = 4.87), benzylamine (pK b = 4.66), and piperidine (pK b = 2.78) are much more basic than aniline (pK b = 9.37; Scheme 1a). [15] Notably,b oth catalyst systems favor the formation of the linear amides from olefins and aliphatic amines.In contrast, the formation of the branched amides from carbonylation reactions is more challenging because of the increase in steric effects for the olefin insertion into the palladiumhydride bond to form the secondary carbon palladium intermediates E (Scheme 1b). To overcome this problem, Huang and co-workers developed an elegant strategy to utilize aminals as surrogates of aliphatic amines.…”

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confidence: 99%

Selective Palladium‐Catalyzed Aminocarbonylation of Olefins to Branched Amides

Liu

Spannenberg

et al. 2016

Angewandte Chemie

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Ag eneral and efficient protocol for iso-selective aminocarbonylation of olefins with aliphatic amines has been developed for the first time.Key to the success for this process is the use of aspecific 2-phosphino-substituted pyrrole ligand in the presence of PdX 2 (X = halide) as ap re-catalyst. Bulk industrial and functionalizedo lefins react with various aliphatic amines,i ncluding amino-acid derivatives,t og ive the corresponding branched amides generally in good yields (up to 99 %) and regioselectivities (b/l up to 99:1).Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: http://dx.

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Rhodium catalyzed one-step hydroamidation of cyclopentadiene and dicyclopentadiene

Cited by 18 publications

References 24 publications

Rhodium-catalyzed hydroaminomethylation of cyclopentadiene

Rhodium-catalyzed hydroaminomethylation of cyclopentadiene

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

Selective Palladium‐Catalyzed Aminocarbonylation of Olefins to Branched Amides

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