Direct amination of ethylene by zeolite catalysis

Deeba, Michel; Ford, Michael E.; Johnson, Thomas A.

doi:10.1039/c39870000562

Cited by 50 publications

(25 citation statements)

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“…Indeed several zeolite-based heterogeneous catalysts have been reported for this transformation at high temperatures and pressures [174][175][176][177][178]. As presented earlier, computational approaches using ammonia as a substrate have been used for catalyst design and also mechanistic investigations [172].…”

Section: Hydroamination With Ammoniamentioning

confidence: 99%

Transition‐Metal‐Catalyzed Hydroamination Reactions

Schafer

Yim

Yonson

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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Section: Hydroamination With Ammoniamentioning

confidence: 99%

Transition‐Metal‐Catalyzed Hydroamination Reactions

Schafer

Yim

Yonson

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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“…Hydroamination has been realized with alkali metal amides,2 lanthanide metallocene complexes,3 or acidic zeolites,4 but these approaches suffer from a number of limitations, most notably poor functional group compatibility. Ru(II),5 Rh(III),6 and Pt(II)7 complexes catalyze the hydroamination of ethylene and, in one case, 1-hexene8 with carboxamides or alkyl or aryl amines, but these transformations require forcing conditions and are of extremely limited scope 9.…”

mentioning

confidence: 99%

Intermolecular Hydroamination of Ethylene and 1-Alkenes with Cyclic Ureas Catalyzed by Achiral and Chiral Gold(I) Complexes

2009

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The intermolecular hydroamination of unactivated alkenes remains an important, unsolved challenge in catalysis.1 Hydroamination has been realized with alkali metal amides,2 lanthanide metallocene complexes,3 or acidic zeolites,4 but these approaches suffer from a number of limitations, most notably poor functional group compatibility. Ru(II),5 Rh(III),6 and Pt(II)7 complexes catalyze the hydroamination of ethylene and, in one case, 1-hexene8 with carboxamides or alkyl or aryl amines, but these transformations require forcing conditions and are of extremely limited scope.9 Although electrophilic gold(I)-10 and platinum(II) triflate11 complexes have been reported to catalyze the intermolecular hydroamination of unactivated alkenes with sulfonamides, these transformations are catalyzed with equal or greater efficiency by Brønsted acids and the metal-catalyzed reactions display behavior consistent with Brønsted acid catalysis.12 -14 Given the challenges associated with the intermolecular hydroamination of unactivated alkenes, it is not surprising that the enantioselective intermolecular hydroamination of unactivated alkenes remains unknown.15 , 16 Here we report the Markovnikov-selective gold(I)-catalyzed hydroamination of ethylene and 1-alkenes with cyclic ureas and the unprecedented enantioselective hydroamination of unactivated 1-alkenes with up to 78% ee.We have recently reported the room temperature intramolecular hydroamination of γ-and δ-alkenyl ureas catalyzed by a mixture of a gold(I) N-heterocyclic carbene (NHC) complex and AgOTf. 17 The mild reaction conditions and the absence of an acid-catalyzed reaction pathway17 pointed to the potential development of a corresponding intermolecular process. However, attempts to realize the hydroamination of ethylene with acyclic ureas catalyzed by gold NHC complexes were uniformly unsuccessful. Conversely, cyclic ureas, employed in combination with a gold o-biphenyl phosphine precatalyst led to efficient hydroamination of ethylene. As an example, treatment of 1-methyl-imidazolidin-2-one (1) (0.4 M) with ethylene (120 psi) and a catalytic 1:1 mixture of (2a)AuCl [2a = P(t-Bu) 2 o-biphenyl] and AgOTf (5 mol %) in dioxane at 100 °C for 24 h led to isolation of 1-ethyl-3-methyl-imidazolidin-2-one (3) in 99% yield (Table 1, entry 1). In addition to 1, a number of cyclic ureas and 2-oxazolidinone reacted with ethylene at 100 °C to give the corresponding N-ethyl derivatives in good yield (Table 1, entries 5,6,7,10). 18 Extension of gold(I)-catalyzed hydroamination to include 1-alkenes was encouraging, but also revealed the limitations of the (2a)AuCl/AgOTf catalyst system. Gold(I)-catalyzed reaction of propene or 1-butene with cyclic ureas at 100 °C led to Markovnikov hydroamination in good yield with high regioselectivity, but extended reaction time and/or higher catalyst loading was rwidenho@chem.duke.edu .

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“…Small to medium pore size zeolites, such as H-clinoptilolite, H-offretite or H-erionite, are efficient for the hydroamination of ethylene [51][52][53][54]. Ethylene and NH3 react at 360°C and 50 bar over H-clinoptilolite to give EtNH 2 only (11.4% conversion).…”

Section: Acid Catalysismentioning

confidence: 99%