R)-1-[(1R)-1-(Dicyclohexylphosphino) ethyl]-2-(diphenylphosphino)-ferrocene and (2S)-1-[(1R)-1-(Dicyclohexylphosphino) ethyl]-2-(diphenylphosphino)-ferrocene (Josiphos)

Blaser, Hans‐Ulrich; Lotz, Matthias; Platonov, Andrey Yu.

doi:10.1002/047084289x.rn00874.pub2

Cited by 3 publications

(1 citation statement)

References 99 publications

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“…The asymmetric hydrogenation provided identical results in both methanol (Table , entry 5) and isopropanol (Table , entry 6). Inspired by the promising results and given an overall consideration of the yield and enantioselectivity, reaction rate, and commercial availability, as well as the cost of the ligand, we decided to choose the catalyst systems [SL-J006-1 with (COD) 2 RhBF 4 and catASium I with (NBD) 2 RhBF 4 ] for further development. , …”

Section: Results and Discussionmentioning

confidence: 99%

Scalable Asymmetric Synthesis of MK-8998, a T-Type Calcium Channel Antagonist

et al. 2021

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Two scalable and efficient synthetic routes for the synthesis of a T-type calcium channel antagonist MK-8998 were developed from a simple pyridine building block. The key step to set the stereochemistry relied on either chiral rhodium catalyst-mediated asymmetric hydrogenation of an enamide or transamination of an arylketone that provided the corresponding product in high enantioselectivity and high yield.

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Section: Results and Discussionmentioning

confidence: 99%

Scalable Asymmetric Synthesis of MK-8998, a T-Type Calcium Channel Antagonist

et al. 2021

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Modular synthesis of unsymmetric 1,3-diphosphinopropanes through sequential substitution reactions

Headford,

Kuhnel,

et al. 2023

Journal of Organometallic Chemistry

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Dimenthylphosphine P-Oxide as a Synthetic Platform for Bulky and Chiral Ligands with Dimenthylphosphino Donor Groups

et al. 2021

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Attaching di(1R)-menthylphosphino fragments (menthyl = Men = 1R,2S,5R-2-isopropyl-5-methylcyclohex-1-yl) to molecular scaffolds turns them into homochiral, bulky, electron-rich phosphine ligands with proven and potential applications in coordination chemistry and transition-metal catalysis. Dimenthylphosphine P-oxide (Men2POH; 1) is established as a platform chemical toward dimenthylphosphino-containing targets via transformation to the known ligand precursors dimenthylchlorophosphine (4) and dimenthylphosphine (6). Transformations of 1 to dimenthylphosphinyl chloride (5) and dimenthylphosphinic acid (8) are elaborated. A phospha-Michael type 1,4-addition of 1 to p-benzo- or 1,4-naphthoquinone gives the corresponding o-hydroxyaryl(dimenthyl)phosphine oxides. Deprotonation of 1 with n-BuLi provides a phosphinyl nucleophile, whose reactions with alkyl halides or 1,n-dihaloalkanes provide tertiary alkyl dimenthylphosphine oxides or 1,n-bis(dimenthylphosphino)alkane bis(P-oxides) 10a–c, respectively. As an example, oxide 10b was deoxygenated to the diphosphine Men2P(CH2)3PMen2 (11) and characterized via the square-planar complex [(Men2P(CH2)3PMen2)PdCl2] (12). A selection of P-aryl dimenthylphosphines, including PhP(Men)2 (19) and 2-ClC6H4P(Men)2 (22), as well as the menthyl analogues Men-JohnPhos (21) and Men-SPhos (24), of the respective Buchwald ligands have been prepared. The combination of the secondary phosphine oxide (SPO) 1 with PdCl2 produces halide-bridged [(Men2POH)2Pd2Cl2] (25), mononuclear [(Men2POH)2PdCl2] (26), or the halide-bridged pseudochelate complex [(Men2PO···H···OPMen2)2Pd2Cl2] (27), depending on the reaction stoichiometry and conditions, all of which have been crystallographically characterized. The new ligands 1, 19, 21, 22, and 24 and complexes 25 and 26 have been evaluated in model palladium-catalyzed C–C- and C–N-fragment coupling reactions and found to display specific reactivity profiles due to the presence of the menthyl groups. Ligand 22 in particular catalyzed an asymmetric biaryl-forming coupling to give 2-methoxy-1,1′-binaphthalene with an er of up to 93:7.

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R)-1-[(1R)-1-(Dicyclohexylphosphino) ethyl]-2-(diphenylphosphino)-ferrocene and (2S)-1-[(1R)-1-(Dicyclohexylphosphino) ethyl]-2-(diphenylphosphino)-ferrocene (Josiphos)

Cited by 3 publications

References 99 publications

Scalable Asymmetric Synthesis of MK-8998, a T-Type Calcium Channel Antagonist

Scalable Asymmetric Synthesis of MK-8998, a T-Type Calcium Channel Antagonist

Modular synthesis of unsymmetric 1,3-diphosphinopropanes through sequential substitution reactions

Dimenthylphosphine P-Oxide as a Synthetic Platform for Bulky and Chiral Ligands with Dimenthylphosphino Donor Groups

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