Palladium-Catalyzed Allylation/Benzylation of H-Phosphinate Esters with Alcohols

Fers-Lidou, Anthony; Berger, Olivier; Montchamp, Jean‐Luc

doi:10.3390/molecules21101295

Cited by 11 publications

(5 citation statements)

References 17 publications

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“…However, it required an extended reaction time and two portions of catalyst to reach completion. For comparison, the reaction of PhP(O)(OBu)H gives a 99 % isolated yield after 24 h at reflux and with 2 mol % Pd [16] …”

Section: Resultsmentioning

confidence: 99%

Synthesis of Adamantyl H‐Phosphinate Esters

2021

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Adamantyl H‐phosphinate esters have been described by Leclaire, Giordano, and coworkers as “universal precursors of P‐stereogenic compounds” after resolution by chiral HPLC, because these esters resist racemization during displacement with organometallics. In that work, the racemic esters were prepared from phosphorus trichloride or dichlorophosphines (RPCl2). We decided to investigate alternative methods for the preparation of these important precursors. Esterification methods included EDC, PivCl, and T3P. A protocol to avoid chromatographic purification was also developed and used for multigram‐scale synthesis. Finally, adamantyl hypophosphite 1‐AdOP(O)H2 was also prepared and used in the synthesis adamantyl H‐phosphinate esters, thereby providing an alternative to the esterification of H‐phosphinic acids, although 1‐AdOP(O)H2 was much less reactive than other hypophosphite esters.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Adamantyl H‐Phosphinate Esters

2021

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“…Palladium‐catalyzed allylations have become well‐established methods for C−C and C−X bond formation from allylic alcohols and carbon‐ and heteroatom‐based nucleophiles, but are less common for C−P bond generation. Early examples used to construct C−P bonds were reported by the Montchamp groups . In 2006, Montchamp et al.…”

Section: C(sp3)−p Bond Formationmentioning

confidence: 99%

“…Besides hypophosphorous acid (HPA, H 3 PO 2 ) and H ‐phosphinic acids, H ‐phosphinate esters, diethyl H ‐phosphonate and diphenylphosphine oxide were also employed in the Pd‐catalyzed allylation with allylic alcohols . The corresponding allylated phosphinic acid derivatives or phosphine oxides 35 were obtained from cinnamyl alcohol under the catalysis of Pd 2 (dba) 3 /xantphos (Scheme ).…”

Section: C(sp3)−p Bond Formationmentioning

confidence: 99%

Dehydrative Cross‐Coupling and Related Reactions between Alcohols (C−OH) and P(O)−H Compounds for C−P Bond Formation

et al. 2019

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In recent decades, reactions of inexpensive and abundantly available alcohols (C−OH) with nucleophilic P(O)−H compounds, leading to the construction of C−P bonds, have emerged as one of the most efficient strategies as it is an atom‐economical and environmental benign approach with water as the only by‐product. Various organophosphorus compounds bearing C(sp3)−P, C(aryl)−P and C(alkenyl)−P bonds have been achieved via this direct dehydrative cross‐couplings under Brønsted or Lewis acid catalysis. This review article aims to summarize the recent advances in such dehydrative and related C−P bond forming strategies, to briefly discuss the reaction mechanisms and challenges, and to outline synthetic opportunities that are still open.

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“…10 We found that our palladium-catalyzed cross-coupling of allylic alcohols previously described with H-phosphinic acids 14 is also successful on H-phosphinate esters. 15 Thus, reaction of (R P )-2 with an equimolar amount of cinnamyl alcohol takes place smoothly to produce (R P )-4 in excellent yield and complete stereospecificity (eqn (1)).…”

Section: Menthyl(hydroxymethyl)phosphinatesmentioning

confidence: 99%

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

Berger

Montchamp

2016

Org. Biomol. Chem.

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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.

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Palladium-Catalyzed Allylation/Benzylation of H-Phosphinate Esters with Alcohols

Cited by 11 publications

References 17 publications

Synthesis of Adamantyl H‐Phosphinate Esters

Synthesis of Adamantyl H‐Phosphinate Esters

Dehydrative Cross‐Coupling and Related Reactions between Alcohols (C−OH) and P(O)−H Compounds for C−P Bond Formation

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

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