Novel, Very Strong, Uncharged Auxiliary Bases; Design and Synthesis of Monomeric and Polymer‐Bound Triaminoiminophosphorane Bases of Broadly Varied Steric Demand

The synthesis and properties of a number of very strong iminophosphorane bases up to an extremely high level of steric hindrance are described. They cover a range of ca. 4 pK units in basicity and a range of more than 11 orders of magnitude in their rates of methylation with methyl iodide. Most of the systems are readily prepared in up to molar quantities, conveniently recovered from their salts and are of high chemical and thermal stability. Crystal structures were determined in order to parametrize a force field, which is utilized in molecular modeling studies offering a rationalization of the observed differences in steric hindrance and basicity. Depending on the degree of steric protection of the basic center, these novel bases are proposed as unprecedented, versatile auxiliary bases in E2 eliminations and in reactions involving deprotonation in the presence of more or less strong electrophiles.

[1]  W. Schnick,et al.  Synthesis and Crystal Structure of the First Tetraaminophosphonium Salt P(NH2)4I , 1994 .

[2]  W. Schnick,et al.  Synthese und Kristallstruktur des ersten Tetraaminophosphonium‐Salzes P(NH2)4I, , 1994 .

[3]  K. Peters,et al.  How Strong and How Hindered Can Uncharged Phosphazene Bases Be , 1993 .

[4]  H. Schnering,et al.  Wie stark und wie gehindert können ungeladene Phosphazenbasen sein , 1993 .

[5]  W. Fessner,et al.  The Pagodane Route to Dodecahedranes Unsaturated (Hyperstable) and Saturated Bissecododecahedranes , 1992 .

[6]  R. Weiss,et al.  ELEKTROSTATISCHE AKTIVIERUNG VON NUCLEOFUGEN : KATIONISCHE ABGANGSGRUPPEN , 1992 .

[7]  R. Weiss,et al.  Electrostatic Activation of Nucleofuges: Cationic Leaving Groups , 1992 .

[8]  T. Allmendinger.  Ethyl phenylsulfinyl fluoroacetate, a new and versatile reagent for the preparation of α-fluoro-α,β-unsaturated carboxylic acid esters , 1991 .

[9]  Reinhurd Schwesinger.  Starke ungeladene Stickstoffbasen , 1990 .

[10]  A. Iribarren,et al.  New synthetic routes to protected purine 2'-O-methylriboside-3'-O- phosphoramidites using a novel alkylation procedure , 1990, Nucleic Acids Res..

[11]  H. Prinzbach,et al.  Unsaturated 1,4‐cis and 1,4‐trans‐Diaminotetradeoxycycloheptites—Enantiomerically Pure, Polyfunctionalized Tropa Derivatives by Enzymatic Hydrolysis , 1989 .

[12]  H. Prinzbach,et al.  Ungesättigte 1,4‐cis‐ und 1,4‐trans‐Diaminotetradesoxycycloheptite – enantiomerenreine, polyfunktionalisierte Tropa‐Derivate durch enzymatische Hydrolyse , 1989 .

[13]  L. Knothe,et al.  Aminoglycoside antibiotics ― Enantiomerically pure sporamine building blocks , 1989 .

[14]  R. Alder.  Strain effects on amine basicities , 1989 .

[15]  H. Prinzbach,et al.  Die Pagodan‐Route zu Dodecahedranen: Chemie und Struktur von Bissecododecahedranen , 1989 .

[16]  D. Hunkler,et al.  The Pagodane Route to Dodecahedranes: Chemistry and Structure of Bissecododecahedranes , 1989 .

[17]  I. Hermecz.  Chemistry of Diazabicycloundecene (DBU) and Other Pyrimidoazepines , 1988 .

[18]  K. Peters,et al.  Novel, Very Strongly Basic, Pentacyclic “Proton Sponges” with Vinamidine Structure , 1987 .

[19]  R. Schwesinger,et al.  Peralkylated Polyaminophosphazenes— Extremely Strong, Neutral Nitrogen Bases , 1987 .

[20]  R. Schwesinger.  Tricyclic 2,4‐Diaminovinamidines– Readily Accessible, Very Strong CHN Bases , 1987 .

[21]  H. Schnering,et al.  Neuartige, sehr stark basische, pentacyclische „Protonenschwämme”︁ mit Vinamidinstruktur , 1987 .

[22]  R. Schwesinger,et al.  Peralkylierte Polyaminophosphazene ‐extrem starke neutrale Stickstoffbasen , 1987 .

[23]  R. Schwesinger.  Tricyclische 2,4‐Diaminovinamidine — leicht zugängliche, sehr starke CHN‐Basen , 1987 .

[24]  T. Netscher,et al.  Tert-butyl- and 2,2,2-trifluoro-1,1-diphenylethane-sulfonates -hindrance of SO-scission in SN2-substitution reactions , 1987 .

[25]  C. Rüchardt,et al.  The Synthetic Potential of the Isocyanide‐Cyanide Rearrangement , 1987 .

[26]  F. Montforts,et al.  Total Synthesis of (±)‐Bonellin Dimethyl Ester , 1985 .

[27]  F. Montforts,et al.  Totalsynthese von (±)-Bonellin-dimethylester , 1985 .

[28]  J. Gandler,et al.  The E2 transition state: elimination reactions of 2-(2,4-dinitrophenyl)ethyl halides , 1984 .

[29]  F. Bordwell,et al.  Donor-atom effects on relative E2 rate constants for reactions of anions with cyclohexyl bromide , 1982 .

[30]  R. Appel,et al.  [Chlortris(dimethylamino)phosphonium]-chlorosulfit, ein schonendes Kondensationsmittel bei Peptidsynthesen , 1981 .

[31]  G. .. Martin,et al.  Etude par resonance magnétique multinucléaire d'intermédiaires réactionnels électrophiles. Partie 8. Action des acides de Lewis chlorés COCl2, POCl3, (CH3)2N=CHCl+Cl− et Cl2 sur l'hexaméthylphosphotriamide (HMPT) , 1980 .

[32]  K. Imahori,et al.  Substrate binding characteristics of the active site of spermidine dehydrogenase from Serratia marcescens. , 1979, Journal of biochemistry.

[33]  B. Castro,et al.  The reaction of hexamethyl phosphoric triamide (HMPT) with phosphoryl chloride : A reexamination. Application to a novel preparation of BOP reagent for peptide coupling , 1979 .

[34]  Norman L. Allinger,et al.  Conformational analysis. 130. MM2. A hydrocarbon force field utilizing V1 and V2 torsional terms , 1977 .

[35]  P. Heimbach,et al.  Control of the Nickel‐Catalyzed Cooligomerization of Butadiene with Schiff Bases by Cocatalysts , 1977 .

[36]  R. Appel,et al.  Ein Diazadiphosphetidin mit ringstabilisiertem „Pentaamidophosphor” , 1977 .

[37]  C. K. Johnson,et al.  OR TEP-II: a FORTRAN Thermal-Ellipsoid Plot Program for crystal structure illustrations , 1976 .

[38]  C. Glidewell.  Cyclophosphazen-Bildung durch „anomale Kirsanov-Reaktion” , 1975 .

[39]  C. Glidewell.  Formation of Cyclopolyphosphazenes in an “Anomalous Kirsanov Reaction” , 1975 .

[40]  K. Gloe,et al.  Darstellung von Diäthylamino‐diamino‐chloro‐ und Bis‐(dimethylamino)‐amino‐chloro‐phosphoniumchlorid , 1975 .

[41]  J. Goubeau,et al.  Darstellung und Schwingungsspektren von Verbindungen des Typus X3PNCH3 , 1974 .

[42]  J. Holubek,et al.  Ganglionic blocking agents. XV. Synthesis and activity of some tertiary hexylamines , 1970 .

[43]  V. Gutmann,et al.  Homologe Alkyliminophosphorsäuretrichloride und deren Ammonolyse , 1966 .

[44]  J. Coetzee,et al.  Properties of Bases in Acetonitrile as Solvent. IV. Proton Acceptor Power and Homoconjugation of Mono- and Diamines , 1965 .

[45]  K. Eiter,et al.  ber zwei neue Verfahren zur Einfhrung der Propinyliden-Gruppe , 1965 .

[46]  K. G. Flynn,et al.  Kinetics and Mechanism of the Reaction between Phenyl Isocyanate and Alcohols. Strong Base Catalysis and Deuterium Isotope Effects , 1963 .

[47]  S. Hünig,et al.  Basenstärke und Alkylierungsgeschwindigkeit aliphatischer, tertiärer Amine , 1958 .

[48]  A. Mckay,et al.  PREPARATION AND CHEMISTRY OF Δ8-HEXAHYDRO-1,4,8-PYRIMIDAZOLE, Δ9-1,5,9-TRIAZABICYCLO(4.4.0)DECENE, AND Δ9-1,4,9-TRIAZABICYGLO(5.3.0)DECENE , 1957 .

[49]  H. Brown,et al.  2,6-DI-BUTYLPYRIDINE—AN UNUSUAL PYRIDINE BASE , 1953 .