N-versus O-silylation in cis-[(tBuHN)OP(μ-NtBu)2PO(NHtBu)] and [Me2Si(μ-NtBu)2PO(NHPh)]. Solid-state structures of their silylation products, of co-crystalline cis-[(tBuHN)OP(μ-NtBu)2PO(NHtBu)], and of {[Me2Si(μ-NtBu)2PO(N(SiMe3)Ph)]VCl3}

Haagenson, Dana C.; Lief, Graham R.; Stahl, Lothar; Staples, Richard J.

doi:10.1016/j.jorganchem.2008.05.023

Cited by 16 publications

(7 citation statements)

References 36 publications

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“…[20][21][22] Recently,t hese species have experienced as low but steady renaissance,and the chemistry of cyclodiphosphazane compounds is regaining momentum within the main group arena. This is illustrated by their implementation in nontraditional areas where these species had little influence,such as catalysts for organic synthesis, [23][24][25] antitumor drugs, [26,27] and small molecule activation. [28,29] Thevast majority of structures comprising P III atoms and/ or their applications have been based on disubstituted cyclodiphosphazane monomeric species (Figure 1, type m III ).…”

Section: Introductionmentioning

confidence: 99%

N‐Bridged Acyclic Trimeric Poly‐Cyclodiphosphazanes: Highly Tuneable Cyclodiphosphazane Building Blocks

et al. 2020

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We have synthesized ac ompletely new family of acyclic trimeric cyclodiphosphazane compounds comprising NH, N i Pr,N t Bu and NPh bridging groups.Inaddition, the first NH-bridged acyclic dimeric cyclophosphazane has been produced. The trimeric species display highly tuneable characteristics so that the distance between the terminal N(H)R moieties can be readily modulated by the steric bulk present in the bridging groups (ranging from % 6t o% 10). Moreover, these species exhibit pronounced topological changes when aw eak non-bonding NH•••p aryl interaction is introduced. Finally,t he NH-bridged chloride binding affinities have been calculated and benchmarked along with the existing experimental data available for monomeric cyclodiphosphazanes. Our results underscore these species as promising hydrogen bond donors for supramolecular host-guest applications.

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Section: Introductionmentioning

confidence: 99%

N‐Bridged Acyclic Trimeric Poly‐Cyclodiphosphazanes: Highly Tuneable Cyclodiphosphazane Building Blocks

et al. 2020

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“…1) are saturated four-membered P 2 N 2 heterocycles that can easily be synthesized with different substitution patterns on phosphorus and nitrogen from commercially available amines and PCl 3 . While achiral P III/V -cyclodiphospazanes have been studied as ligands in transition-metal chemistry [22–23], only two examples of cyclodiphosphazanes as catalysts in asymmetric reactions are known; Chakravarty et al [24] tested an ansa -bridged BINOL-based P V -cyclodiphosphazane in the asymmetric reduction of acetophenone with BH 3 (5–8% ee), while Gade et al [25] recently introduced BINOL-based P III -cyclodiphosphazane ligands to transition-metal catalysis (up to 84% ee). We anticipated that by incorporation of a chiral amido-scaffold into bis(amido)cyclodiphosphazanes ( cis -[R'NHP(S)(μ-NR)] 2 ), bulky and conformationally constrained bidentate HB catalysts with an improved H-acidity should be accessible.…”

Section: Introductionmentioning

confidence: 99%

New hydrogen-bonding organocatalysts: Chiral cyclophosphazanes and phosphorus amides as catalysts for asymmetric Michael additions

Klare¹,

Neudörfl²,

Goldfuß³

2014

Beilstein J. Org. Chem.

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SummaryTen novel hydrogen-bonding catalysts based on open-chain PV-amides of BINOL and chinchona alkaloids as well as three catalysts based on rigid cis-PV-cyclodiphosphazane amides of N 1,N 1-dimethylcyclohexane-1,2-diamine have been developed. Employed in the asymmetric Michael addition of 2-hydroxynaphthoquinone to β-nitrostyrene, the open-chain 9-epi-aminochinchona-based phosphorus amides show a high catalytic activity with almost quantitative yields of up to 98% and enantiomeric excesses of up to 51%. The cyclodiphosphazane catalysts show the same high activity and give improved enantiomeric excesses of up to 75%, thus representing the first successful application of a cyclodiphosphazane in enantioselective organocatalysis. DFT computations reveal high hydrogen-bonding strengths of cyclodiphosphazane PV-amides compared to urea-based catalysts. Experimental results and computations on the enantiodetermining step with cis-cyclodiphosphazane 14a suggest a strong bidentate H-bond activation of the nitrostyrene substrate by the catalyst.

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“…Recently, these species have experienced a slow but steady renaissance, and the chemistry of cyclodiphosphazane compounds is regaining momentum within the main group arena. This is illustrated by their implementation in non‐traditional areas where these species had little influence, such as catalysts for organic synthesis, [23–25] antitumor drugs, [26, 27] and small molecule activation [28, 29] …”

Section: Introductionmentioning

confidence: 99%

“…[20][21][22] Recently,t hese species have experienced as low but steady renaissance,and the chemistry of cyclodiphosphazane compounds is regaining momentum within the main group arena. This is illustrated by their implementation in non-traditional areas where these species had little influence,such as catalysts for organic synthesis, [23][24][25] antitumor drugs, [26,27] and small molecule activation. [28,29] Thevast majority of structures comprising P III atoms and/ or their applications have been based on disubstituted cyclodiphosphazane monomeric species (Figure 1, type m III ).…”

Section: Introductionmentioning

confidence: 99%

N‐Bridged Acyclic Trimeric Poly‐Cyclodiphosphazanes: Highly Tuneable Cyclodiphosphazane Building Blocks

et al. 2020

View full text Add to dashboard Cite

We have synthesized ac ompletely new family of acyclic trimeric cyclodiphosphazane compounds comprising NH, N i Pr,N t Bu and NPh bridging groups.Inaddition, the first NH-bridged acyclic dimeric cyclophosphazane has been produced. The trimeric species displayh ighly tuneable characteristics so that the distance between the terminal N(H)R moieties can be readily modulated by the steric bulk present in the bridging groups (ranging from % 6to% 10). Moreover,these species exhibit pronounced topological changes when aw eak non-bonding NH•••p aryl interaction is introduced. Finally,the NH-bridged chloride binding affinities have been calculated and benchmarked along with the existing experimental data available for monomeric cyclodiphosphazanes.O ur results underscore these species as promising hydrogen bond donors for supramolecular host-guest applications.

show abstract

N-versus O-silylation in cis-[(tBuHN)OP(μ-NtBu)2PO(NHtBu)] and [Me2Si(μ-NtBu)2PO(NHPh)]. Solid-state structures of their silylation products, of co-crystalline cis-[(tBuHN)OP(μ-NtBu)2PO(NHtBu)], and of {[Me2Si(μ-NtBu)2PO(N(SiMe3)Ph)]VCl3}

Cited by 16 publications

References 36 publications

N‐Bridged Acyclic Trimeric Poly‐Cyclodiphosphazanes: Highly Tuneable Cyclodiphosphazane Building Blocks

N‐Bridged Acyclic Trimeric Poly‐Cyclodiphosphazanes: Highly Tuneable Cyclodiphosphazane Building Blocks

New hydrogen-bonding organocatalysts: Chiral cyclophosphazanes and phosphorus amides as catalysts for asymmetric Michael additions

N‐Bridged Acyclic Trimeric Poly‐Cyclodiphosphazanes: Highly Tuneable Cyclodiphosphazane Building Blocks

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