Mild Arbuzov reactions of phosphonous acids

Thottathil, John K.; Przybyla, Claire A.; Moniot, Jerome L.

doi:10.1016/s0040-4039(01)81506-9

Cited by 46 publications

(24 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Finally, the reaction of unactivated (bromomethyl)phthalimide was examined using the more common silylation (HMDS/TMSCl) 17 from the diastereoisomeric mixture (mother liquor) of 2. As shown in eqn (2), the overall yield was reasonable and the stereoselectivity excellent.…”

Section: Menthyl(hydroxymethyl)phosphinatesmentioning

confidence: 99%

General synthesis of P-stereogenic compounds: the menthyl phosphinate approach

Berger

Montchamp

2016

Org. Biomol. Chem.

View full text Add to dashboard Cite

Easily prepared menthyl phosphinates of high diastereoisomeric purity provide versatile intermediates for the synthesis of P-stereogenic compounds. Previous efforts starting about fifty years ago have been hampered by a lack of generality so the menthyl route has been nearly abandoned. Herein we provide a general solution to this long-standing problem and describe a general synthesis of menthyl H-phosphinate and disubstituted phosphinate esters. The method to prepare these versatile precursors relies on a simple and inexpensive process avoiding the use of phosphorus trichloride, Grignard reagents, and complicated cryogenic crystallizations. Established protocols can then be employed to synthesize P-stereogenic secondary and tertiary phosphine oxides and therefore P-stereogenic phosphine ligands.

show abstract

Section: Menthyl(hydroxymethyl)phosphinatesmentioning

confidence: 99%

General synthesis of P-stereogenic compounds: the menthyl phosphinate approach

Berger

Montchamp

2016

Org. Biomol. Chem.

View full text Add to dashboard Cite

show abstract

“…The answer to the question of why this process is limited to Ph 2 PÀOR compounds is not clear. Tentatively, this could be accounted for in terms of a pronounced tendency to form the structure Ph 2 P À P(O)Ph 2 (21).…”

Section: Synthesis Of [Ar 2 Pr 2 ]mentioning

confidence: 99%

Studies on the Efficient Generation of PhosphorusCarbon Bonds via a Rearrangement of P^III Esters Catalysed by Trimethylhalosilanes

Dąbkowski

Ozarek

Olejniczak

et al. 2009

Chemistry A European J

View full text Add to dashboard Cite

Halotrimethylsilanes Me(3)SiX (X = Br, I) catalyse rearrangements of tricoordinate phosphorus esters R'R''P-OR into the corresponding phosphoryl systems R'R''P(O)R. This provides a simple and efficient route to a variety of structures containing phosphorus-carbon bonds, under mild conditions and with good yields. The reaction mechanism was investigated in detail by (31)P NMR spectroscopy and independent synthesis of the reaction intermediates. It has been demonstrated that the primary products of this catalytic reaction are halogeno P(III) structures R'R''PX and silyl ethers ROSiMe(3) and that they subsequently react to give the corresponding phosphorus silyl esters-Me(3)SiOPR'R''-and alkyl halides RX. At higher temperatures these intermediates then react to form R'R''P(O)R compounds. This paper also features the surprising observation that when esters Ph(2)POR and halotrimethylsilanes Me(3)SiX (X = Br, I) are used in 2:1 ratio, phosphonium salts Ph(2)R(2)P(+)X(-) and trimethylsilyl diphenylphosphinate--Ph(2)P(O)OSiMe(3)--are formed as the major products. Experimental evidence indicates that the mechanisms of both reactions are fundamentally different from that of the Michaelis-Arbuzov reaction. Me(3)SiCl is not reactive and this paper explains why.

show abstract

“…A similar sequence of "group introduction" has been explored subsequently to generate a series of phosphinothricin analogues (37), derivatised at the phosphinylmethyl position in order to optimise E.I. interactions with glutamine synthetase [26], employing a "mild Arbuzov" approach to C-P bond formation [27,28] (Scheme 5b). Treatment of the methyl-derivatised phosphinic acids 38 with hexamethyldisilazane yielded the requisite bis(trimethylsilyl) phosphonites 39 [28] in order to elicit low temperature, Arbuzov-type substitutions with methyl (2S)-N-benzyloxycarbonyl-2-amino-4-iodobutyrate (40) [26].…”

Section: Scheme 3 [17]mentioning

confidence: 99%

ω -Phosphinyl-α -Amino Acids: Synthesis, and Development towards Use as Therapeutic Agents

Wardle¹,

Bligh²,

Hudson³

2007

COC

View full text Add to dashboard Cite

Literature publications (up to September 2006) concerning the synthesis of -phosphinyl--amino acids and their development towards use as therapeutic agents are reviewed. General and asymmetric methodologies for the preparation of straight-chain examples are described, including AP3-7 modulators of glutamate-responsive excitatory amino acid (EAA) receptors (i.e. ionotropic NMDA-, and metabotropic GrpIII mGlu-receptors), and the glutamate synthetase inhibitor phosphinothricin. Focusing primarily on the development of methods for introducing phosphonate and aminocarboxylate functions to the appropriate scaffold, approaches to conformationally constrained -phosphinyl--amino acids are also investigated, along with their relevance to the development of therapeutic regimens towards neurodegenerative disorders.

show abstract

Mild Arbuzov reactions of phosphonous acids

Cited by 46 publications

References 3 publications

General synthesis of P-stereogenic compounds: the menthyl phosphinate approach

General synthesis of P-stereogenic compounds: the menthyl phosphinate approach

Studies on the Efficient Generation of PhosphorusCarbon Bonds via a Rearrangement of P^III Esters Catalysed by Trimethylhalosilanes

ω -Phosphinyl-α -Amino Acids: Synthesis, and Development towards Use as Therapeutic Agents

Contact Info

Product

Resources

About

Mild Arbuzov reactions of phosphonous acids

Cited by 46 publications

References 3 publications

General synthesis of P-stereogenic compounds: the menthyl phosphinate approach

General synthesis of P-stereogenic compounds: the menthyl phosphinate approach

Studies on the Efficient Generation of PhosphorusCarbon Bonds via a Rearrangement of PIII Esters Catalysed by Trimethylhalosilanes

&#969; -Phosphinyl-&#945; -Amino Acids: Synthesis, and Development towards Use as Therapeutic Agents

Contact Info

Product

Resources

About

Studies on the Efficient Generation of PhosphorusCarbon Bonds via a Rearrangement of P^III Esters Catalysed by Trimethylhalosilanes

ω -Phosphinyl-α -Amino Acids: Synthesis, and Development towards Use as Therapeutic Agents