The Phospha‐Michael Addition in Organic Synthesis

Enders, Dieter; Saint‐Dizier, Alexandre; Lannou, Marie‐Isabelle; Lenzen, Achim

doi:10.1002/ejoc.200500593

Cited by 341 publications

(209 citation statements)

References 115 publications

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“…The structure of 19a is chiral and exhibits a C 2 crystallographic axis spanning the ring and both (boranato)diphenylphosphino groups, which are in trans relative configuration (Figure 1). (14), N-C1-C2-P -100.70(12), C1-C2-P-C13 -163.77 (12). C2-C1-N-C1 i -7.28 (8).…”

Section: Methodsmentioning

confidence: 99%

“…10 Usually, the stereoselective synthesis of chiral organophosphorus compounds with P-C bond formation was performed using chlorophosphines or phosphides as electrophilic or nucleophilic reagents, respectively. 9,11 In the last decade, the asymmetric hydrophosphination 12,13 and phospha-Michael addition 14 have also emerged as powerful methodologies for the synthesis of functional derivatives such as chiral organophosphorus compounds, that hold promise for applications in asymmetric catalysis. In this last case, typical reactions of Michael acceptor with free secondary phosphines or their oxide, sulfur or other borane derivatives, were achieved either in basic conditions or by heating.…”

Section: Introductionmentioning

confidence: 99%

“…In this last case, typical reactions of Michael acceptor with free secondary phosphines or their oxide, sulfur or other borane derivatives, were achieved either in basic conditions or by heating. 14,15 On the other hand, the asymmetric phospha-Michael addition could also be performed using chiral transition metal catalysts [16][17][18] or organocatalysts. [19][20][21] Among the nucleophilic phosphorus reagents, the silylphosphines have recently retained the attention because these compounds are considered more electron-rich than the parent secondary phosphines due to the electrodonating effect of the silicon moiety.…”

Section: Introductionmentioning

confidence: 99%

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P-Chirogenic silylphosphine-boranes: synthesis and phospha-Michael reactions

Bonnefille¹,

Tessier²,

Cattey³

et al. 2015

Arkivoc

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Chiral and achiral silylphosphine-boranes were prepared in high yields by reaction of phosphide boranes with halogenosilanes. Their reaction at room temperature with Michael acceptors afforded 1,4-addition products as silylenol ether or ketone derivatives in good to excellent yields. In the case of the 2,3-dihalogeno-maleimides, the double addition of silylphosphine-borane led to the corresponding trans-diphosphine-boranes in 86% yield. Noteworthy, the reaction of Pchirogenic silylphosphine-boranes with enones afforded the phospha-Michael adducts without racemization at the P-center. While the silylphosphine-boranes have been scarcely described so far, these compounds demonstrate their great interest for the synthesis of chiral and achiral functionalized organophosphorus compounds.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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P-Chirogenic silylphosphine-boranes: synthesis and phospha-Michael reactions

Bonnefille¹,

Tessier²,

Cattey³

et al. 2015

Arkivoc

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“…1 β-aminophosphonic acids, in particular, exhibit antibacterial, enzyme inhibitory and anti-HIV properties. 2 Although numerous methods are available in the literature for the synthesis of β-nitro/aminophosphonates, [2][3] there are only handful of approaches for the asymmetric synthesis of such compounds. [3][4] This is despite the fact that introduction of chirality in the flexible aminophosphonic acid chain is likely to enhance its diverse and potent biological properties.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective conjugate addition of dialkyl phosphites to nitroalkenes

Rai

Namboothiri

2008

Tetrahedron: Asymmetry

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“…Recently, Tian and co-workers have developed an efficient alternative way to Henry reaction involving a deprotonation of a nitroalkane with the zwitterionic ester enolate to form a nitronate and a subsequent reaction with aldehyde. 4 The conjugate addition of a dialkylphosphonate anion to electron-deficient olefins provided an efficient way to alkylsubstituted phosphonates; 5,6 however, the method required usually a strong base 6a,b,d-h or somewhat drastic conditions. Thus, an alternative way has been used more widely involving the use of trialkyl phosphite.…”

mentioning

confidence: 99%

An Efficient Conjugate Addition of Dialkyl Phosphite to Electron-Deficient Olefins: The Use of a Nucleophilic Organocatalyst to Form a Strong Base

Kim¹,

Kim²,

Kim³

et al. 2013

Bulletin of the Korean Chemical Society

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The formation of a zwitterionic species between electrondeficient olefins and tertiary amine or phosphine is a pivotal and the starting point for the Morita-Baylis-Hillman (MBH) reaction 1 and Rauhut-Currier (RC) reaction. 2 A subsequent 1,2-addition of the zwitterion I, which was generated from methyl acrylate as an example, to aldehyde and a proton movement furnished the Morita-Baylis-Hillman adduct, whereas a conjugate addition to electron-deficient olefins is the Rauhut-Currier reaction, as shown in Scheme 1. Basically, the zwitterion is an ester enolate and could act as a base. 3,4In this respect, White and Baizer reported a phosphinecatalyzed conjugate addition of 2-nitropropane to various electron-deficient olefins, as also shown in Scheme 1.3a Toste and co-workers reported a phosphine-catalyzed conjugate addition of alcohol or water to electron-deficient olefins. Later, Pedduri and Williamson have applied the concept to make tetrahydrofurans.3c Vallribera and co-workers also reported the conjugate addition of β-dicarbonyl compounds to electron-deficient olefins.3d The mechanism of the conjugate additions likely involves the zwitterion I behaving as a base to deprotonate the nitroalkane, alcohol, water and β-dicarbonyl; the nitronate, alkoxide, hydroxide or the enolate of β-dicarbonyl then undergoes the following conjugate additions to electron-deficient olefins. Recently, Tian and co-workers have developed an efficient alternative way to Henry reaction involving a deprotonation of a nitroalkane with the zwitterionic ester enolate to form a nitronate and a subsequent reaction with aldehyde. 4The conjugate addition of a dialkylphosphonate anion to electron-deficient olefins provided an efficient way to alkylsubstituted phosphonates;5,6 however, the method required usually a strong base 6a,b,d-h or somewhat drastic conditions. Thus, an alternative way has been used more widely involving the use of trialkyl phosphite. 7 The reaction between electron-deficient olefins such as methyl acrylate and trialkyl phosphite generated a zwitterionic species at elevated temperature. A subsequent Michaelis-Arbuzov type rearrangement in the presence of phenol afforded the desired alkyl phosphonate, as shown in Scheme 2. In these respects, we presumed that the conjugate addition reactions catalyzed by a nucleophilic organocatalyst such as tributylphosphine could be applied for the synthesis of alkyl phosphonate, as also shown in Scheme 2.At the outset of our experiment we examined the reaction of methyl acrylate and diethyl phosphite in the presence of various nucleophilic catalyst including DABCO, n-Bu 3 P and PPh 3 in CH 3 CN. The use of DABCO (10 mol %, rt, 6 days) did not produce 2a in any trace amount.3b The use of n-Bu 3 P (20 mol %, rt, 2 h) produced 2a in good yield (72%), whereas the reaction in the presence of PPh 3 (20 mol %, reflux, 24 h) produced 2a in a trace amount (< 5%).3b Further studies revealed that the use of 5-10 mol % of n-Bu 3 P showed cleaner reaction and increased the yield of 2a.The reaction mecha...

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The Phospha‐Michael Addition in Organic Synthesis

Cited by 341 publications

References 115 publications

P-Chirogenic silylphosphine-boranes: synthesis and phospha-Michael reactions

P-Chirogenic silylphosphine-boranes: synthesis and phospha-Michael reactions

Enantioselective conjugate addition of dialkyl phosphites to nitroalkenes

An Efficient Conjugate Addition of Dialkyl Phosphite to Electron-Deficient Olefins: The Use of a Nucleophilic Organocatalyst to Form a Strong Base

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