Novel Bis(1,3,2-diazaphospholidine) Ligands for Asymmetric Catalysis

Arribas, Inmaculada; Álvarez, Eleuterio; Pizzano, Antonio

doi:10.1021/om400185q

Cited by 12 publications

(6 citation statements)

References 40 publications

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“…In 2013, Pizzano 57 introduced chiral bis- N , N ′-diphenyl-1,3,2-diazaphospholidine (NP-PN) as a DACH ligand L7 . Upon addition to the cationic norbornadiene Rh(I) complex [Rh(NBD) 2 ]BF 4 , the active catalyst DACH [Rh(NBD)(NP-PN)]BF 4 is generated.…”

Section: Catalytic Asymmetric Hydrogenation Of Alkenesmentioning

confidence: 99%

See 1 more Smart Citation

1,2-trans-Diaminocyclohexane (DACH) in Asymmetric Catalysis: Nearing Fifty Years of Faithful Service and Counting

Hanessian,

Mishra

2024

Synthesis

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This review highlights the use of DACH as a versatile ligand in catalytic asymmetric transformations providing mechanistic rationales and relevant comments presented in chronological order for each of the 21 reaction types with references up to December 25, 2023. Intended to be as practically comprehensive as possible, this review assembles useful examples of using DACH as a ligand in organocatalytic or as metal complexes in asymmetric transformations. The resulting enantiomerically enriched, if not pure, chiral non-racemic small molecules are of great utility as value added intermediates in the total synthesis of natural products, in the design and synthesis of medicinally important compounds, and in other areas in organic and bioorganic chemistry where chirality plays a role. The graphic image depicts Spartacus with his arms folded in the same sense of chirality as (R,R)-DACH.1 Introduction2 DACH: A Brief Historical Narrative3 Catalytic Asymmetric Hydrogenation of Alkenes4 Catalytic Asymmetric Dihydroxylation of Alkenes5 Catalytic Asymmetric Sulfoxidation and Sulfimidation6 Catalytic Asymmetric 1,4-Conjugate Addition6.1 Using Jacobsen’s DACH Metal–salen Complexes as Catalysts6.2 Using Takemoto’s Bifunctional H-Bonding DACH Thiourea Organocatalyst6.3 Using DACH Ni(II) Complexes as Catalysts6.4 Using DACH H-Bonding Catalysis7 Catalytic Asymmetric Epoxidation of Alkenes8 Catalytic Asymmetric Claisen Rearrangement9 Catalytic Asymmetric 1,2-Nucleophilic Addition to Carbonyl Compounds9.1 Catalytic Asymmetric Addition of Dialkylzinc to Aldehydes and Ketones9.2 Catalytic Asymmetric Alkynylation of Aldehydes and Ketones9.3 Catalytic Asymmetric Addition of Cyanide to Aldehydes and Ketones10 Catalytic Asymmetric Allylic Alkylation11 Catalytic Asymmetric Cyclopropanation of Alkenes12 Catalytic Asymmetric Cycloaddition Reactions13 Catalytic Asymmetric Aziridination of Alkenes14 Catalytic Asymmetric Hydrogenation of Prochiral Ketones and Imines15 Catalytic Asymmetric Aldol Reactions16 Catalytic Asymmetric Opening of Small Ring Systems16.1 Desymmetrization of meso-Epoxides and meso-Aziridines16.2 Kinetic Resolution of Racemic Epoxides16.3 Enantioselective Addition of CO2 to Epoxides16.4 Enantioselective Ring Opening of Oxetanes17 Catalytic Asymmetric Strecker Reactions18 Catalytic Asymmetric Mannich Reactions19 Catalytic Asymmetric Henry and Aza-Henry Reactions20 Catalytic Asymmetric Morita–Baylis–Hillman and Rauhut–Currier Reactions21 Catalytic Asymmetric Petasis Reactions22 Organocatalytic Asymmetric Cascade Reactions23 Miscellaneous Catalytic Reactions24 Conclusion and Outlook25 DACH Catalysts and Ligands List

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Section: Catalytic Asymmetric Hydrogenation Of Alkenesmentioning

confidence: 99%

“…It was reported that the active catalyst completed the hydrogenation of 19 with 100% conversion at S/C = 100 at 24 h. The L7 ligand was also used for hydroformylation of vinyl acetates with excellent regioselectivity and moderate enantioselectivity (up to 65%). 57…”

Section: Catalytic Asymmetric Hydrogenation Of Alkenesmentioning

confidence: 99%

1,2-trans-Diaminocyclohexane (DACH) in Asymmetric Catalysis: Nearing Fifty Years of Faithful Service and Counting

Hanessian,

Mishra

2024

Synthesis

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“…Consequently, the development of more efficient ligands for a range of catalytic processes is still a vital research topic. During the past decade, new families of chiral phosphines, including monodentate phosphines, − bis(aminophosphine)-type ligands, − phosphino-phosphite (P-OP), − phosphino-phosphoramidite, − spiroketal , or supramolecular-type − biphosphines, and others, , have found widespread use in the rhodium-catalyzed AH of N -acyl enamines . Among these, the past decade has witnessed the development of P -stereogenic electron-rich alkyl phosphines as highly proficient ligands. ,,− Figure shows the most relevant P -stereogenic ligands used in the rhodium-catalyzed AH of benchmark enamides (Table ).…”

Section: Asymmetric Hydrogenation Of Enamidesmentioning

confidence: 99%

Recent Advances in the Enantioselective Synthesis of Chiral Amines via Transition Metal-Catalyzed Asymmetric Hydrogenation

2021

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Chiral amines are key structural motifs present in a wide variety of natural products, drugs, and other biologically active compounds. During the past decade, significant advances have been made with respect to the enantioselective synthesis of chiral amines, many of them based on catalytic asymmetric hydrogenation (AH). The present review covers the use of AH in the synthesis of chiral amines bearing a stereogenic center either in the α, β, or γ position with respect to the nitrogen atom, reported from 2010 to 2020. Therefore, we provide an overview of the recent advances in the AH of imines, enamides, enamines, allyl amines, and N-heteroaromatic compounds.

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“…To finalize this section, we consider a unique bis(1,3,2diazaphospholidine) ligand used for the asymmetric Rh hydrogenation of a methyl acetamidoacrylate (MAA) to give N-acetylalanine (Scheme 20). 48 Unfortunately, the authors only selected one substrate for their study, i.e., MAA, but they screened four different precatalysts (Scheme 20A). All of the reactions were quantitative and in favor of the R-enantiomer.…”

Section: ■ Introductionmentioning

confidence: 99%

Recent Advances in Asymmetric Hydrogenation Catalysis Utilizing Spiro and Other Rigid C-Stereogenic Phosphine Ligands

2021

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Transition-metal-catalyzed asymmetric reactions have been a powerful tool in organic synthesis for many years. The design of chiral ligands with the right configuration is fundamental to induce high regio- and stereoselectivity to catalytic reactions and to achieve high turnover numbers and high yields. A challenge is the control of prochiral centers with similar electronic properties in a similar steric environment within the same molecule. Over the last 10 years, a range of novel rigid C-stereogenic chiral phosphine ligands has been developed and successfully applied in various types of asymmetric transformations. Many of these ligands are of a di-, tri-, or multidentate nature. The purpose of this Perspective is to highlight recent synthetic achievements (since 2010) with spiro-phosphines and other rigid phosphines and discuss some mechanistic aspects of the catalytic reactions.

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Novel Bis(1,3,2-diazaphospholidine) Ligands for Asymmetric Catalysis

Cited by 12 publications

References 40 publications

1,2-trans-Diaminocyclohexane (DACH) in Asymmetric Catalysis: Nearing Fifty Years of Faithful Service and Counting

1,2-trans-Diaminocyclohexane (DACH) in Asymmetric Catalysis: Nearing Fifty Years of Faithful Service and Counting

Recent Advances in the Enantioselective Synthesis of Chiral Amines via Transition Metal-Catalyzed Asymmetric Hydrogenation

Recent Advances in Asymmetric Hydrogenation Catalysis Utilizing Spiro and Other Rigid C-Stereogenic Phosphine Ligands

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