Asymmetric synthesis of organophosphorus compounds using H–P reagents derived from chiral alcohols

Gbubele, Joseph Daniel; Olszewski, Tomasz K.

doi:10.1039/d1ob00124h

Cited by 42 publications

(15 citation statements)

References 105 publications

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“…Next, I combines with O 2 to produce peroxyl radical II , which generates hydroperoxide III via abstraction of a hydrogen atom from 2a , together with a regeneration of radical I . Then, III undergoes the reduction process to form unstable hemiacetal IV , which in situ generates 4-hydroxybutanal V . , Finally, the Pudovik-type reaction of 1a with V results in the formation of 3aa . To further understand the reaction mechanism, the standard reaction of 1a and 2a with the addition of 4-nitrobenzaldehyde was carried out (see the Supporting Information for details).…”

supporting

confidence: 90%

Visible-Light-Induced α-C(sp³)–H Phosphinylation of Unactivated Ethers under Photocatalyst- and Additive-Free Conditions

Liu

et al. 2022

J. Org. Chem.

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A photocatalyst- and additive-free visible-light-induced α-C(sp3)–H phosphinylation of unactivated ethers involving a C–O bond cleavage with molecular oxygen as the sole oxidant at room temperature has been achieved. This method provides a sustainable access to α-hydroxyphosphine oxides in up to 88% yield with good functional group compatibility under mild and neutral conditions (34 examples). Moreover, the subsequent two-step conversion of the resulting dihydroxy diarylphosphine oxides afforded α-phosphinylated cyclic ethers in good overall yields (10 examples).

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supporting

confidence: 90%

Visible-Light-Induced α-C(sp³)–H Phosphinylation of Unactivated Ethers under Photocatalyst- and Additive-Free Conditions

Liu

et al. 2022

J. Org. Chem.

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“…The intramolecular cyclization of in situ-generated primary phosphines with an alkenyl group was achieved to give phospholanes and phosphorinanes, which were isolated as boron complexes. Further studies on organophosphorus compounds with a binaphthyloxy group as key precursors [57] for P-stereogenic organophosphorus compounds are in progress.…”

Section: Discussionmentioning

confidence: 99%

Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes

et al. 2021

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Organophosphorus compounds with stereogenic phosphorus and carbon atoms have received increasing attention. In this regards, primary phosphines with a stereogenic carbon atom adjacent to the phosphorus atom were synthesized by the reduction in phosphonates and phosphonoselenoates with a binaphthyl group. Their oxidized products, i.e., phosphine oxides with a stereogenic tetrasubstituted carbon atom, were found to undergo BEt3-mediated radical addition to cyclohexene to give P-stereogenic secondary phosphine oxides with a diastereoselectivity of 91:9. The products were characterized by ordinary analytical methods, such as Fourier transform infrared spectroscopy; 1H, 13C, and 31P NMR spectroscopies; and mass spectroscopy. Computational studies on the phosphorus-centered radical species and the obtained product implied that the thermodynamically stable radical and the adduct may be formed as a major diastereomer. The radical addition to a range of alkenes took place in an anti-Markovnikov fashion to give P-stereogenic secondary phosphine oxides. A variety of functional groups in the alkenes were tolerated under the reaction conditions to afford secondary phosphine oxides in moderate yields. Primary phosphines with an alkenyl group, which were generated in situ, underwent intramolecular cyclization to give five- and six-membered cyclic phosphines in high yields after protection by BH3.

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“…In 1996, Shibasaki’s pioneering work on the asymmetric hydrophosphonylation of aldehydes catalyzed by the Al-Li-BINOL complex was disclosed in both excellent yields (up to 95% yield) and enantioselectivities (up to 90% enantiomeric excess (ee)) . Hereafter, two modules of chiral catalysts were designed to apply for the transformation: one is the metal-based chiral catalyst, involving complexes containing Al, Fe, Zn, Cu, Ni, and RE, and the other is organocatalyst, such as chiral cinchona–thiourea, chiral cinchona–diaminomethylenemalononitrile (DMM), P -spirocyclic chiral tetraaminophosphonium salt, and so on . As a whole, the metal-based catalytic asymmetric hydrophosphonylations of aldehydes and ketones require relatively lower catalyst loading and milder conditions in many cases.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Hydrophosphonylation of α,β-Unsaturated Ketones Catalyzed by Rare-Earth Metal Complexes Bearing Trost Ligands

Song,

Sun,

et al. 2022

J. Org. Chem.

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Chiral dinuclear rare-earth metal complexes RE 2 L n 2 (n = 1, RE = Y(1), Eu(2), Nd(3), La(4), Gd(5); n = 2, RE = Eu(6), Gd( 7)) stabilized by the corresponding Trost ligandswere prepared and three unknown complexes 5−7 were characterized by X-ray diffraction analysis. The chiral rare-earth metal complexes 1−7 displayed high reactivity in the asymmetric hydrophosphonylation of α,β-unsaturated ketones, and 5 mol % of complex 7 together with 10 mol % of chiral diamine (1S,2S)-1,2-cyclohexanediamine were proved to be the optimal catalyst combination. Various hydrophosphonylation products with excellent yields and high to excellent enantiomeric excess (ee) values were obtained in toluene (up to 99% yield, >99% ee).

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Asymmetric synthesis of organophosphorus compounds using H–P reagents derived from chiral alcohols

Abstract: Chiral organophosphorus compounds, especially those containing C-stereogenic carbons in the proximity of the phosphorus atom, are known for their unique properties and have found wide applications that span from medicinal...

Cited by 42 publications

References 105 publications

Visible-Light-Induced α-C(sp³)–H Phosphinylation of Unactivated Ethers under Photocatalyst- and Additive-Free Conditions

Visible-Light-Induced α-C(sp³)–H Phosphinylation of Unactivated Ethers under Photocatalyst- and Additive-Free Conditions

Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes

Asymmetric Hydrophosphonylation of α,β-Unsaturated Ketones Catalyzed by Rare-Earth Metal Complexes Bearing Trost Ligands

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Asymmetric synthesis of organophosphorus compounds using H–P reagents derived from chiral alcohols

Abstract: Chiral organophosphorus compounds, especially those containing C-stereogenic carbons in the proximity of the phosphorus atom, are known for their unique properties and have found wide applications that span from medicinal...

Cited by 42 publications

References 105 publications

Visible-Light-Induced α-C(sp3)–H Phosphinylation of Unactivated Ethers under Photocatalyst- and Additive-Free Conditions

Visible-Light-Induced α-C(sp3)–H Phosphinylation of Unactivated Ethers under Photocatalyst- and Additive-Free Conditions

Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes

Asymmetric Hydrophosphonylation of α,β-Unsaturated Ketones Catalyzed by Rare-Earth Metal Complexes Bearing Trost Ligands

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Visible-Light-Induced α-C(sp³)–H Phosphinylation of Unactivated Ethers under Photocatalyst- and Additive-Free Conditions

Visible-Light-Induced α-C(sp³)–H Phosphinylation of Unactivated Ethers under Photocatalyst- and Additive-Free Conditions