A new method for 1,2-diamination of alkenes using cyclopentadienylnitrosylcobalt dimer/NO/LiAlH4

Becker, Paul; White, Mary Ann; Bergman, Robert G.

doi:10.1021/ja00537a046

Cited by 98 publications

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“…(1)]. 2, 5a–c More recently this chemistry has been used to develop a method for CC bond formation 5d,e. In addition, the reaction of K[IrCl 5 (NO)] with alkenes to yield iridium nitrosoalkane complexes,6 and the reaction of [TpRuCl 2 (NO)] (Tp=tris(pyrazolyl)borate) with 2‐vinylpyridine to yield a nitrosoalkene complex have been reported 7…”

Section: Methodsmentioning

confidence: 99%

Synthesis of [RuCl₂(NO)₂(THF)] and its Double CN Bond‐Forming Reactions with Alkenes

2011

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While the activation of relatively inert gases such as N 2 and CO with organometallic complexes remains a topic of intense investigation, methods for controlling the reactivity of nitric oxide at transition-metal centers have received considerably less attention. [1][2][3] For example, the migratory insertion of NO into metal-alkyl or metal-aryl bonds has been observed in only a handful of metal complexes, [3] despite the analogous reaction of CO dominating its organometallic chemistry and being the key step in many homogeneous catalytic processes. Although the paucity of studies in this field may be a reflection of the often complicated background reactivity of NO, [4] the potential to develop selective reactions incorporating NO that form new carbon-nitrogen bonds represents an attractive approach in organic synthesis.It is in this context that we are interested in the ligandbased reaction of metal nitrosyl complexes with alkenes.[5] In the absence of metal coordination the reaction chemistry of NO with alkenes is unruly.[4] Furthermore, only a few transition-metal complexes have been shown to promote this reaction selectively. Thus, inspired by an early finding of Brunner and Loskot, we demonstrated in the 1980s that [{CpCo(NO)} 2 ], NO and strained or alkyl-substituted alkenes react cleanly to form the corresponding dinitrosoalkane complexes [1, Eq. (1)].[2, 5a-c] More recently this chemistry has been used to develop a method for C À C bond formation. [5d,e] In addition, the reaction of K[IrCl 5 (NO)] with alkenes to yield iridium nitrosoalkane complexes, [6] and the reaction of [TpRuCl 2 (NO)] (Tp = tris(pyrazolyl)borate) with 2-vinylpyridine to yield a nitrosoalkene complex have been reported. [7] In spite of the above reactions, there are not many C À N bond-forming reactions of metal nitrosyls and double additions remain especially rare. We now report an example of this type of reactivity with the novel dinitrosyl complex [RuCl 2 (NO) 2 (THF)], which binds alkenes to the nitrosyl nitrogen atoms at room temperature in the presence of an additional neutral chelating ligand, L 2 . (2) as a brown crystalline solid in 88 % yield (Scheme 1). In the solid state, 2 possesses near-perfect square-based pyramidal geometry at the metal (t = 0.04), [8] with one bent NO ligand occupying the apical site and one linear NO ligand occupying an equatorial site trans to coordinated THF (Figure 1). The remaining trans-disposed coordination sites of the basal plane are occupied by chloride ligands.Complex 2 represents a rare example of a metal dinitrosyl complex possessing both linear and bent nitric oxide ligands in the solid state. The first structurally characterized example of such a complex, [RuCl(NO) 2 (PPh 3 ) 2 ]PF 6 (3), was reported by Eisenberg and co-workers and, while cationic, provides an important point of comparison. [9,10] The bending of apical nitrosyl ligands in five-coordinate complexes has been the topic of theoretical discussions.[11] Although ruthenium-nitrogen bond lengths (3, 1.743(20) ; 2, 1.727(5)...

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Section: Methodsmentioning

confidence: 99%

Synthesis of [RuCl₂(NO)₂(THF)] and its Double CN Bond‐Forming Reactions with Alkenes

2011

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“…A particularly attractive route to the synthesis of vicinal diamines and amino alcohols is through the direct difunctionalization of alkenes. Early approaches to alkene difunctionalization by Backväll,3 Barluenga,4 Sharpless,5 and others6 employed stoichiometric amounts of a heavy metal complex or salt. The hydroxyamination of alkenes was subsequently rendered catalytic in osmium7 and eventually, both catalytic and enantioselective 8.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular diamination and alkoxyamination of alkenes with N-sulfonyl ureas employing N-iodosuccinimide

Widenhoefer

2010

Tetrahedron

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Reaction of N-δ-alkenyl-N'-sulfonyl urea 1 with N-iodosuccinimde (NIS; 2 equiv) and a catalytic amount of AgOTf (20 mol %) at room temperature led to intramolecular alkoxyamination to form bicyclic isourea 2a in 95% isolated yield. In comparison, reaction of 1 with NIS and sodium bicarbonate (1 equiv) at room temperature led to isolation of bicyclic imidazolidin-2-one 2b in 91% yield. These NIS-mediated alkoxyamination and diamination protocols were effective for a range of N-δ-alkenyl-N'-sulfonyl ureas to form the corresponding heterobicyclic compounds in good yield with high chemoselectivity and good to excellent diastereoselectivity.

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“…On the other hand, several catalytic routes have also been investigated. Various metal-free [4,5] or metal-mediated [6,7] processes have been developed and metal-catalyzed diaminations have also been reported. [8] Moreover, although transition metal-catalyzed hydroamination [9,10] and oxidative dehydroamination [11,12] have been extensively developed in recent years, transition metal-catalyzed alkene 1,2-diamination is still a challenge.…”

Section: Introductionmentioning

confidence: 99%

DFT studies on the mechanism of Pd(II)‐catalyzed intermolecular 1,2‐diamination of conjugated dienes

Shen

Zhang

et al. 2008

J of Physical Organic Chem

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The reaction mechanism of the palladium(II)-catalyzed addition of urea to dienes to form 1,2-diamine was studied using the B3LYP density functional theory (DFT) method. The results indicate that the first C-N s-bond formation is the rate-determining step, and that the covalent bonds are formed favorably by the terminal carbon atoms of dienes and nitrogen atom. The Pd(NCMe)-catalyst may significantly lower the energy barrier of the rate-determining step from the nonligand Pd(II)-catalyst counterpart. The results are in strong support of a recent experiment.

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A new method for 1,2-diamination of alkenes using cyclopentadienylnitrosylcobalt dimer/NO/LiAlH4

Cited by 98 publications

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Synthesis of [RuCl₂(NO)₂(THF)] and its Double CN Bond‐Forming Reactions with Alkenes

Synthesis of [RuCl₂(NO)₂(THF)] and its Double CN Bond‐Forming Reactions with Alkenes

Intramolecular diamination and alkoxyamination of alkenes with N-sulfonyl ureas employing N-iodosuccinimide

DFT studies on the mechanism of Pd(II)‐catalyzed intermolecular 1,2‐diamination of conjugated dienes

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A new method for 1,2-diamination of alkenes using cyclopentadienylnitrosylcobalt dimer/NO/LiAlH4

Cited by 98 publications

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Synthesis of [RuCl2(NO)2(THF)] and its Double CN Bond‐Forming Reactions with Alkenes

Synthesis of [RuCl2(NO)2(THF)] and its Double CN Bond‐Forming Reactions with Alkenes

Intramolecular diamination and alkoxyamination of alkenes with N-sulfonyl ureas employing N-iodosuccinimide

DFT studies on the mechanism of Pd(II)‐catalyzed intermolecular 1,2‐diamination of conjugated dienes

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Synthesis of [RuCl₂(NO)₂(THF)] and its Double CN Bond‐Forming Reactions with Alkenes

Synthesis of [RuCl₂(NO)₂(THF)] and its Double CN Bond‐Forming Reactions with Alkenes