Protonen‐induzierte Umlagerung eines Oxaphosphirankomplexes

Pérez, Janaina Marinas; Helten, Holger; Donnadieu, Bruno; Reed, Christopher A.; Streubel, Rainer

doi:10.1002/ange.200906825

Angewandte Chemie

2010

DOI: 10.1002/ange.200906825

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Protonen‐induzierte Umlagerung eines Oxaphosphirankomplexes

Janaina Marinas Pérez

Holger Helten

Bruno Donnadieu

et al.

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Cited by 16 publications

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“…This new concept could also be applied to the synthesis of a 2,3-dihydro-1,3-azaphosphete and a 3 H -1,3-azaphosphole complex via insertion of an isonitrile or an alkyne, respectively . Furthermore, this chemistry could easily be extended to oxaphosphirane and azaphosphiridine complexes, thus firmly establishing a click chemistry concept to the field of phosphorus heterocyclic chemistry.…”

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When Sterics Overcome Electronics: An Unusual Haptotropic P→N Pentacarbonyltungsten Shift

et al. 2010

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Acid-induced ring expansion of 2H-azaphosphirene complexes 1a-c with HCN is described. These reactions yielded 2H-1,4,2-diazaphosphole complexes 2a-c as a mixture with their κN-coordination isomers 3a-c in different ratios, depending upon the steric demand of the C 3 -substituent on the diazaphosphole ring. DFT calculations revealed that the isomerization can proceed in one step via a haptotropic PfN W(CO) 5 shift. When a mixture of 2b and 3b was heated in acetonitrile, complete decomplexation with formation of 2H-1,4,2-diazaphosphole 5 was observed. Reaction of 2b and 3b with tetra-n-butylammonium fluoride in the presence of [Et 3 NH][OTf] led to complete desilylation of the P-CH(SiMe 3 ) 2 substituent and formation of complex 6, showing only κP-coordination. In addition to NMR, IR, and UV/vis spectra, the single-crystal X-ray diffraction structures of 2a,b and 6 are discussed.

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When Sterics Overcome Electronics: An Unusual Haptotropic P→N Pentacarbonyltungsten Shift

et al. 2010

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Umpolung of Methylenephosphonium Ions in Their Manganese Half‐Sandwich Complexes and Application to the Synthesis of Chiral Phosphorus‐Containing Ligand Scaffolds

et al. 2015

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Half-sandwich manganese methylenephosphonium complexes [Cp(CO) 2 Mn(h 2 -R 2 P=C(H)Ph)]BF 4 were obtained in high yield through as traightforwardr eaction sequence involving ac lassical Fischer-type manganese complex and asecondary phosphine as key starting materials.The addition of various nucleophiles (Nu) to these species took place regioselectively at the double-bonded carbon center of the coordinated methylenephosphonium ligand R 2 P + =C(H)Ph to produce the corresponding chiral phosphine complexes [Cp(CO) 2 Mn(k 1 -R 2 PÀC(H)(Ph)Nu)],f rom which the phosphines were ultimately recovered as free entities upon simple irradiation with visible light. The synthetic potential of this umpolung approach is illustrated herein by the preparation of novel chiral pincer-type phosphine-NHC-phosphine ligand architectures.Iminium salts are of utmost importance in organic synthesis, [1] owing in particular to their key role as intermediates in many enantioselective organocatalytic transformations of carbonyl compounds. [2] However,the synthetic utility of their phosphorus analogues,m ethylenephosphonium ions, [3, 4] remains limited to af ew examples of [2+ +2] [4h,j] and [2+ +4] [4b,e,g] cycloaddition, the ene reaction, [4b,e] electrocyclic cyclization with an arene ring, [4e,f] stereoselectiver earrangement to give phosphaalkenes, [4d] and the phospha-Stork reaction. [4l] Whereas the reactivity of iminium salts is governed by the strong electrophilicity of the carbon atom (Scheme 1), the methylenephosphonium salts undergo regioselective addition of nucleophiles (Nu = F À ,C l À ,a nd MeO À ) [3a,b, 4a] at the electropositivep hosphorus center (Scheme 1). In attempts to explore the reactivity of manganese methylenephosphonium complexes [Cp(CO) 2 Mn-(h 2 -R 2 P = C(H)Ph)] BF 4 ,r eadily available from half-sandwich Mn I Fischer carbenes and secondary phosphines as key starting materials,w eo bserved that the coordinated methylenephosphonium moiety undergoes regioselective addition of nucleophiles at the carbon center, thus mimicking the reactivity mode of iminium salts (Scheme 1; in this scheme and thereafter {Mp} = Cp(CO) 2 Mn). This key observation inspired the development of an unconventional synthetic methodology toward aw ide variety of organophosphorous derivatives,a si llustrated herein by as imple route to an ovel family of chiral pincer-type phosphine-NHC-phosphine ligands (NHC = N-heterocyclic carbene).Earlier investigations in our laboratories had previously established that the cationic manganese carbyne [{Mp} + C À Ph] BPh 4 ([2]BPh 4 )r eacts sequentially with diphenylphosphine and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to give the h 1 -phosphinocarbene complex 3a,which undergoes facile CO insertion to form the h 3 -phosphinoketene complex 4a (see structures in Scheme 2). [5] We have now found that further protonation of 4a with HBF 4 ·OEt 2 leads to the quantitative formation of the cationic complex [5a] + with a h 2 -methylenephosphonium ligand (Scheme 2). [6,7] This reaction is ar are example of c...

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Cycloaddition von P‐C‐Einfachbindungen: Stereoselektive Bildung von Benzo‐1,3,6,2‐trioxaphosphepinkomplexen über einen ditopischen Van‐der‐Waals‐Komplex

et al. 2016

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Protonen‐induzierte Umlagerung eines Oxaphosphirankomplexes

Cited by 16 publications

References 71 publications

When Sterics Overcome Electronics: An Unusual Haptotropic P→N Pentacarbonyltungsten Shift

When Sterics Overcome Electronics: An Unusual Haptotropic P→N Pentacarbonyltungsten Shift

Umpolung of Methylenephosphonium Ions in Their Manganese Half‐Sandwich Complexes and Application to the Synthesis of Chiral Phosphorus‐Containing Ligand Scaffolds

Cycloaddition von P‐C‐Einfachbindungen: Stereoselektive Bildung von Benzo‐1,3,6,2‐trioxaphosphepinkomplexen über einen ditopischen Van‐der‐Waals‐Komplex

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