501381-03-9Relevant academic research and scientific papers
l-Menthol-Assisted Synthesis of P-Stereogenic Phosphinous Acid Amides and Phosphine-Boranes
W?odarczyk, Adam,Kozio?, Anna E.,Stankevi?, Marek
, p. 1589 - 1600 (2018/04/20)
Diastereomerically pure phenylphosphonous acid-borane l-menthyl ester N,N-diethylamide was obtained through the fractional crystallization of a diastereomeric mixture of compounds synthesized from PhPCl2, l-menthol, diethylamine, and BH3·THF. Treatment of racemic or diastereomerically pure phenylphosphonous acid-borane derivatives with sodium in liquid ammonia followed by the addition of an electrophile led to the formation of phosphinous acid-amides. Surprisingly, these compounds undergo preferential P–N bond cleavage under Birch reduction conditions.
Intramolecular nucleophilic substitution of ω-haloalkylphosphine derivatives
Pawe?, Wo?nicki,Korzeniowska, Ewelina,Stankevic, Marek
, p. 10271 - 10296 (2018/02/27)
ω-Haloalkylphosphine derivatives undergo the intramolecular nucleophilic substitution reaction upon treatment with a strong base, yielding either cycloalkylphosphine derivatives or heterocyclic phosphine derivatives. The selectivity of the cyclization of
In situ dearomatisation/alkylation of arylphosphane derivatives
Stankevic, Marek,Wojcik, Karolina,Jaklinska, Magdalena,Pietrusiewicz, K. Michal
, p. 2521 - 2534 (2012/06/01)
The dearomatisation of aryldialkylphosphane-boranes and aryldialkylphosphane oxides under Birch reduction conditions, followed by treatment with reactive alkyl halides, provides the corresponding α-functionalised (cyclohexa-1,4-dien-3-yl)phosphane derivatives. This reaction offers a method of choice for the synthesis of bulky (cyclohexadienyl)phosphanes.
Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride
Rajendran, Kamalraj V.,Gilheany, Declan G.
, p. 817 - 819 (2012/02/03)
A variety of phosphine oxides and sulfides can be efficiently converted directly to the corresponding phosphine boranes using oxalyl chloride followed by sodium borohydride. Optically active P-stereogenic phosphine oxides can be converted stereospecifically to phosphine boranes with inversion of configuration by treatment with Meerwein's salt followed by sodium borohydride.
7-Phosphanorbornenium borohydrides: A powerful route to functional secondary phosphine-borane complexes
Tian, Rongqiang,Mathey, Francois
scheme or table, p. 1873 - 1874 (2010/06/14)
The reaction of phosphanorbornenium triflates with sodium borohydride gives the secondary phosphine-borane complexes by reductive cleavage of the two P-C bonds of the bridge. This route is compatible with functionalities such as Cl, CN, CO2Et, and Th.
Reduction of phosphinites, phosphinates, and related species with DIBAL-H
Busacca, Carl A.,Bartholomeyzik, Teresa,Cheekoori, Sreedhar,Raju, Ravinder,Eriksson, Magnus,Kapadia, Suresh,Saha, Anjan,Zeng, Xingzhong,Senanayake, Chris H.
experimental part, p. 287 - 291 (2009/07/01)
Diisobutylaluminium hydride has been found to be an excellent reducing agent for phosphinites, phosphinates, and chlorophosphines. By performing reductions in situ, direct synthesis of secondary phosphine boranes from Grignard reagents has been achieved without isolation or purification of any intermediates. Georg Thieme Verlag Stuttgart.
Palladium-catalyzed asymmetric phosphination. Enantioselective synthesis of PAMP-BH3, ligand effects on catalysis, and direct observation of the stereochemistry of transmetalation and reductive elimination
Moncarz, Julian R.,Brunker, Tim J.,Jewett, John C.,Orchowski, Michael,Glueck, David S.,Sommer, Roger D.,Lam, Kin-Chung,Incarvito, Christopher D.,Concolino, Thomas E.,Ceccarelli, Christopher,Zakharov, Lev N.,Rheingold, Arnold L.
, p. 3205 - 3221 (2008/10/08)
The complexes Pd(diphos)(o-An)(I) (o-An = o-MeOC6H4; diphos = dppe (3), (S,S)-Chiraphos (4), (R,R)-Me-Duphos (5), (R,S) -t-Bu-Josiphos (6), (R)-Tol-Binap (7)) were prepared. Complex 6 catalyzed the coupling of PH(Me)(Ph)(BH3) (2) with o-AnI in the presence of base to yield PAMP-BH3 (P(Me)(Ph)(o-An)(BH3) (1)) in low enantiomeric excess. The course of stoichiometric reactions of 3-7 with 2 and NaOSiMe3 depended on the diphosphine ligand. Complexes 6 and 7 gave PAMP-BH3 (1) and Pd(0) species; no intermediates were observed. With 3, the intermediate Pd(dppe)(o-An)(P(Me)(Ph)(BH3)) (10) was observed by 31P NMR, while 4 gave the isolable diastereomeric palladium complexes (Sp)-Pd((S,S)-Chiraphos)(o-An)(P(Me)(Ph)(BH3)) (11a) and (RP)-Pd((S,S)-Chiraphos)(o-An)(P(Me)(Ph)(BH3)) (11b), whose absolute configurations were determined by X-ray crystallography after separation. The analogous Pd((R,R)-Me-Duphos)(o-An)(P(Me)(Ph)(BH3)) diastereomers (12a,b) were also separated and isolated. Treatment of 4 with highly enantioenriched 2 (R or S) gave 11a or 11b in high diastereomeric excess with retention of configuration at phosphorus. P-C reductive elimination from either isomer of highly diastereoenriched 11 in the presence of excess diphenylacetylene yielded Pd((S,S)-Chiraphos)(PhC≡CPh) (14) and highly enantioenriched PAMP-BH3 (1), with retention of configuration.
P-H bond activation of primary phosphine-boranes: Access to α-hydroxy and α,α′-dihydroxyphosphine-borane adducts by uncatalyzed hydrophosphination of carbonyl derivatives
Bourumeau, Karine,Gaumont, Annie-Claude,Denis, Jean-Marc
, p. 205 - 213 (2007/10/03)
Primary P-phenyl and P-methyl phosphine-boranes 1 and 2 are prepared by complexation of the free phosphines with BH3 · SMe2. They are stable and can be purified by distillation. Under basic conditions, they lead selectively to secondary alkylphosphine-boranes and under neutral conditions to the corresponding mono- and bis-hydroxyphosphine-boranes 5 and 6. All these new compounds are purified by chromatography on silica gel. A competitive hydroboration induced by the decomplexation of BH3 is observed as a minor process. Conditions for the decomplexation of phosphine-borane adducts are presented.
