Diphosphanes derived from phobane and phosphatrioxa-adamantane: similarities, differences and anomalies.

The homodiphosphanes CgP-PCg (1) and PhobP-PPhob (2) and the heterodiphosphanes CgP-PPhob (3), CgP-PPh(2) (4a), CgP-P(o-Tol)(2) (4b), CgP-PCy(2) (4c), CgP-P(t)Bu(2) (4d), PhobP-PPh(2) (5a), PhobP-P(o-Tol)(2) (5b), PhobP-PCy(2) (5c), PhobP-P(t)Bu(2) (5d) where CgP = 6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-9-yl and PhobP = 9-phosphabicyclo[3.3.1]nonan-9-yl have been prepared from CgP(BH(3))Li or PhobP(BH(3))Li and the appropriate halophosphine. The formation of 1 is remarkably diastereoselective, with the major isomer (97% of the product) assigned to rac-1. Restricted rotation about the P-P bond of the bulky meso-1 is detected by variable temperature (31)P NMR spectroscopy. Diphosphane 3 reacts with BH(3) to give a mixture of CgP(BH(3))-PPhob and CgP-PPhob(BH(3)) which was unexpected in view of the predicted much greater electron-richness of the PhobP site. Each of the diphosphanes was treated with dimethylacetylene dicarboxylate (DMAD) in order to determine their propensity for diphosphination. The homodiphosphanes 1 and 2 did not react with DMAD. The CgP-containing heterodiphosphanes 4a-d all added to DMAD to generate the corresponding cis alkenes CgPCH(CO(2)Me)=CH(CO(2)Me)PR(2) (6a-d) which have been used in situ to form chelate complexes of the type [MCl(2)(diphos)] (7a-d) where M = Pd or Pt. The PhobP-containing heterodiphosphanes 3 and 5a-d react anomalously with DMAD and do not give the products of diphosphination. The X-ray crystal structures of the diphosphanes 2, 3, 4a, and 5a, the monoxide and dioxide of diphosphane 1, and the platinum chelate complex 7c have been determined and their structures are discussed.

[1]  X. Sauvage,et al.  Mixed Isobutylphobane/N‐Heterocyclic Carbene Ruthenium‐ Indenylidene Complexes: Synthesis and Catalytic Evaluation in Olefin Metathesis Reactions , 2010 .

[2]  H. Alper,et al.  Synthesis of dibenzo[b,f][1,4]oxazepin-11(10H)-ones via intramolecular cyclocarbonylation reactions using PdI(2)/Cytop 292 as the catalytic system. , 2010, The Journal of organic chemistry.

[3]  D. Gudat.  Diazaphospholenes: N-heterocyclic phosphines between molecules and Lewis pairs. , 2010, Accounts of chemical research.

[4]  Martin B. Smith,et al.  Versatile routes to selenoether functionalised tertiary phosphines. , 2010, Dalton transactions.

[5]  A. Orpen,et al.  Is restricted M–P rotation a common feature of enantioselective monophos catalysts? An example of restricted Rh–P rotation in a secondary phosphine complex , 2010 .

[6]  S. Duckett,et al.  A parahydrogen based NMR study of Pt catalysed alkyne hydrogenation. , 2010, Dalton transactions.

[7]  M. Hofmann,et al.  Towards spontaneous heterolysis of the homonuclear P-P bond in diphosphines: the case of diazaphospholeniumtriphospholides. , 2010, Chemistry.

[8]  A. Orpen,et al.  Subtleties in asymmetric catalyst structure: the resolution of a 6-phospha-2,4,8-trioxa-adamantane and its applications in asymmetric hydrogenation catalysis. , 2010, Chemical communications.

[9]  J. McNulty,et al.  A synthesis of sulfonamide analogs of platensimycin employing a palladium-mediated carbonylation strategy , 2009 .

[10]  Johannes Weber,et al.  Diphosphines with strongly polarized P-P bonds: hybrids between covalent molecules and donor-acceptor adducts with flexible molecular structures. , 2009, Journal of the American Chemical Society.

[11]  Feng Xu,et al.  Highly efficient asymmetric synthesis of sitagliptin. , 2009, Journal of the American Chemical Society.

[12]  A. Orpen,et al.  Anatomy of phobanes. diastereoselective synthesis of the three isomers of n-butylphobane and a comparison of their donor properties. , 2009, Journal of the American Chemical Society.

[13]  Martin Nieger,et al.  Diphosphination of Electron Poor Alkenes , 2009 .

[14]  Martin Nieger,et al.  Cleavage of Polarized P−P Bonds in N-Heterocyclic Diphosphines in Reactions with Metal Olefin Complexes , 2009 .

[15]  Martin Nieger,et al.  Activation of Polarized Phosphorus–Phosphorus Bonds by Alkynes: Rational Synthesis of Unsymmetrical 1,2-Bisphosphine Ligands and Their Complexes , 2009 .

[16]  S. Nolan,et al.  Ruthenium‐Indenylidene Complexes: Scope in Cross‐Metathesis Transformations , 2008 .

[17]  A. Sadow,et al.  Palladium-catalyzed enantioselective allylic phosphination. , 2008, Angewandte Chemie.

[18]  C. P. Nicolaides,et al.  Homogeneous metathesis for the production of propene from butene , 2008 .

[19]  Martin B. Smith,et al.  Coordination Studies of a New Nonsymmetric Ditertiary Phosphane Bearing a Single Phosphaadamantane Cage , 2008 .

[20]  J. Ellman,et al.  Rh(I)-catalyzed arylation of heterocycles via C-H bond activation: expanded scope through mechanistic insight. , 2008, Journal of the American Chemical Society.

[21]  Martin Nieger,et al.  Increasing the Lability of Polarised Phosphorus–Phosphorus Bonds , 2008 .

[22]  S. Nolan,et al.  Phosphabicyclononane-containing ru complexes: efficient pre-catalysts for olefin metathesis reactions. , 2008, The Journal of organic chemistry.

[23]  S. Otto,et al.  Steric and electronic properties in bicyclic phosphines. Crystal and molecular structures of Se = Phoban-Q (Q = C2, C3Ph, Cy and Ph) , 2007 .

[24]  S. Otto,et al.  Bicyclic phosphines as ligands for cobalt catalysed hydroformylation. Crystal structures of [Co(Phoban[3.3.1]-Q)(CO)3]2 (Q = C2H5, C5H11, C3H6NMe2, C6H11) , 2007 .

[25]  O. Hara,et al.  Synthesis of 2,6-dimethyl-9-aryl-9-phosphabicyclo[3.3.1]nonanes: their application to asymmetric synthesis of chiral tetrahydroquinolines and relatives , 2007 .

[26]  A. Whitwood,et al.  A para-hydrogen investigation of palladium-catalyzed alkyne hydrogenation. , 2007, Journal of the American Chemical Society.

[27]  M. Nieger,et al.  Metal-assisted, reversible phosphinyl phosphination of the carbon-nitrogen triple bond in a nitrile. , 2007, Angewandte Chemie.

[28]  Thomas S. Varley,et al.  Mononuclear and Heterodinuclear Metal Complexes of Nonsymmetric Ditertiary Phosphanes Derived from R2PCH2OH , 2007 .

[29]  H. B. Jonassen,et al.  Metal‐Diolefin Coordination Compounds , 2007 .

[30]  Grant S. Forman,et al.  Mechanistic comparison of ruthenium olefin metathesis catalysts : DFT insight into relative reactivity and decomposition behavior , 2006 .

[31]  Grant S. Forman,et al.  Metathesis of renewable unsaturated fatty acid esters catalysed by a phoban-indenylidene ruthenium catalyst , 2006 .

[32]  A. Orpen,et al.  Stereospecific Diphosphination of Activated Acetylenes: A General Route to Backbone-Functionalized, Chelating 1,2-Diphosphinoethenes , 2006 .

[33]  M. Clarke,et al.  Highly regioselective rhodium-catalysed hydroformylation of unsaturated esters: the first practical method for quaternary selective carbonylation. , 2006, Chemistry.

[34]  Grant S. Forman,et al.  Rotational Isomerism of a Phoban-Derived First-Generation Grubbs Catalyst , 2006 .

[35]  Grant S. Forman,et al.  Tin and iron halogenides as additives in ruthenium-catalyzed olefin metathesis , 2006 .

[36]  R. Morris,et al.  Ketone H2-hydrogenation catalysts: Ruthenium complexes with the headphone-like ligand bis(phosphaadamantyl)propane , 2006 .

[37]  E. Drent,et al.  Highly Selective Halide Anion-Promoted Palladium-Catalyzed Hydroformylation of Internal Alkenes to Linear Alcohols , 2006 .

[38]  D. Williams,et al.  Highly Selective Metathesis of 1-Octene in Ionic Liquids , 2006 .

[39]  Grant S. Forman,et al.  A Convenient System for Improving the Efficiency of First-Generation Ruthenium Olefin Metathesis Catalysts , 2005 .

[40]  S. Blechert,et al.  Unexpected Results of a Turnover Number (TON) Study Utilising Ruthenium‐Based Olefin Metathesis Catalysts , 2005 .

[41]  A. Orpen,et al.  Separation of phobane isomers by selective protonation , 2005 .

[42]  H. Yorimitsu,et al.  Synthesis of (E)-1,2-diphosphanylethene derivatives from alkynes by radical addition of tetraorganodiphosphane generated in situ. , 2005, Angewandte Chemie.

[43]  A. C. Marr,et al.  Phenylphosphatrioxa-adamantanes: bulky, robust, electron-poor ligands that give very efficient rhodium(I) hydroformylation catalysts. , 2005, Dalton transactions.

[44]  A. Orpen,et al.  Nine-Membered Trans Square-Planar Chelates Formed by a bisbi Analogue , 2005 .

[45]  J. McNulty,et al.  Phospha-adamantanes as ligands for organopalladium chemistry: aminations of aryl halides , 2004 .

[46]  E. Alberico,et al.  Chiral diphosphine ligands based on an arene chromium tricarbonyl scaffold: a modular approach to asymmetric hydrogenation , 2004 .

[47]  J. Britten,et al.  Phosphaadamantanes as ligands for palladium catalyzed cross-coupling chemistry: library synthesis, characterization, and screening in the Suzuki coupling of alkyl halides and tosylates containing beta-hydrogens with boronic acids and alkylboranes. , 2004, The Journal of organic chemistry.

[48]  Martin J. Hanton,et al.  A Stable Ruthenium Catalyst for Productive Olefin Metathesis , 2004 .

[49]  Stephan A. Ohnmacht,et al.  Solid-phase Suzuki cross-coupling reactions using a phosphine ligand based on a phospha-adamantane framework , 2004 .

[50]  A. Robertson,et al.  Palladium complexes of 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phenyl-6-phosphaadamantane: synthesis, crystal structure and use in the Suzuki and Sonogashira reactions and the alpha-arylation of ketones. , 2004, The Journal of organic chemistry.

[51]  A. Robertson,et al.  Novel class of tertiary phosphine ligands based on a phospha-adamantane framework and use in the Suzuki cross-coupling reactions of aryl halides under mild conditions. , 2003, Organic letters.

[52]  E. Drent,et al.  Tandem isomerisation–carbonylation catalysis: highly active palladium(II) catalysts for the selective methoxycarbonylation of internal alkenes to linear esters , 2001 .

[53]  O. Hara,et al.  Asymmetric allylic substitution reactions of 2-substituted 2-cycloalkenyl carbonates using 9-PBN coordinated palladium , 2001 .

[54]  He‐Kuan Luo,et al.  Large‐ring P/O chelate nickel complex catalyzed oligomerization of ethylene to linear α‐olefins , 2000 .

[55]  Takeshi Nakano,et al.  ASYMMETRIC ALLYLIC SUBSTITUTION REACTION WITH NITROGEN AND OXYGEN NUCLEOPHILES USING MONODENTATE CHIRAL PHOSPHINE, 9-PBN , 1999 .

[56]  A. Orpen,et al.  Bis(phospha-adamantyl)alkanes: a new class of very bulky diphosphines , 1999 .

[57]  P. Pringle,et al.  A simple procedure for the separation of the catalytically important phosphabicyclononane isomers , 1997 .

[58]  Y. Hamada,et al.  New monodentate chiral phosphine 2,6-dimethyl-9-phenyl-9-phosphabicyclo[3.3.1]nonane(9-PBN): Application to asymmetric allylic substitution reaction , 1996 .

[59]  R. Grubbs,et al.  Safe and Convenient Procedure for Solvent Purification , 1996 .

[60]  V. Gramlich,et al.  Successful Application of a "Forgotten" Phosphine in Asymmetric Catalysis: A 9-Phosphabicyclo[3.3.1]non-9-yl Ferrocene Derivative as Chiral Ligand , 1995 .

[61]  R. Bertani,et al.  Synthesis and spectroscopic investigation of cis and trans isomers of bis(nitrile)dichloroplatinum(II) complexes , 1992 .

[62]  T. V. Harris,et al.  Preparation of a novel phosphorus-phosphorus bonded diphosphine , 1985 .

[63]  B. J. Mulraney,et al.  Synthesis and physical properties of chlorodi(o-totyl)phosphine, lithium di(o-totyl)2P(CH2)nP(o-totyl) (n 1-4, 6, 8) , 1981 .

[64]  P. Garrou.  .DELTA.R-ring contributions to phosphorus-31 NMR parameters of transition-metal-phosphorus chelate complexes , 1981 .

[65]  A. English,et al.  Stereodynamics of tetra-tert-butyldiphosphine. 270 MHz hydrogen-1 and 36.43 MHz phosphorus-31 dynamic nuclear magnetic resonance studies of restricted phosphorus-phosphorus bond rotation , 1976 .

[66]  T. Appleton,et al.  Effect of chelate-ring size on spectroscopic and chemical properties of methylplatinum(II) complexes of the ditertiary phosphines Ph2P[CH2]nPPh2(n= 1,2, or 3) , 1976 .

[67]  W. Mcfarlane,et al.  A phosphorus-31 nuclear magnetic resonance study of tertiary phosphine complexes of platinum(II) , 1967 .

[68]  R. E. Richards,et al.  195 Pt–31P nuclear spin coupling constants and the nature of the trans-effect in platinum complexes , 1966 .