Highly Enantioselective Hydrogenation of
 tetra
 - and
 tri
 -Substituted α,β-Unsaturated Carboxylic Acids with
 oxa
 -Spiro Diphosphine Ligands

Chen, Genqiang; Huang, Jiaming; Lin, Bijin; Shi, Chuan; Zhao, Lingyu; Ma, Baode; Ding, Xiaobing; Yin, Qin; Zhang, Xumu

doi:10.31635/ccschem.020.202000176

Cited by 32 publications

(17 citation statements)

References 57 publications

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“…Various chiral ligands were evaluated in the enantioselective lactonization of 1 a with 1 mol% corresponding gold complexes and 4 mol% AgSbF 6 in CHCl 3 at room temperature for 1 hour. As depicted in Scheme 1, monophosphine ligand ( L1 ), diphosphine ligands ( L2 and L3 [29] ) and commercial P,N ligands ( L4 – L6 ) led to poor enantioselectivity and regioselectivity (0 % to −30 % ee and 2 : 1 to 4 : 1 exo / endo selectivity). However, using bifunctional P,N ligands based on chiral spirocyclic scaffolds ( L7 ‐ L12 ) significantly improved the enantioselectivity and regioselectivity.…”

Section: Resultsmentioning

confidence: 99%

Gold‐Catalyzed Desymmetric Lactonization of Alkynylmalonic Acids Enabled by Chiral Bifunctional P,N ligands

et al. 2022

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Due to the linear coordination nature of gold(I) catalysts, achieving high enantiocontrol in asymmetric gold catalysis is a great challenge. To improve the enantiocontrol of gold catalysis, an ion-pairing strategy was therefore proposed. A series of bifunctional P,N ligands based on chiral spirocyclic and biaryl scaffolds were synthesized and applied in the gold(I)-catalyzed desymmetric lactonization of alkynylmalonic acids. A wide range of chiral lactones containing an α-position quaternary stereocenter were synthesized with high yields, excellent regioselectivity and enantioselectivity under mild reaction conditions. The synthetic utilities of the current reaction were demonstrated by gram-scale synthesis and transformations of chiral lactones. The origin of enantioselectivity and the role of the alcohol additive were elucidated via control experiments and DFT calculations.

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Section: Resultsmentioning

confidence: 99%

Gold‐Catalyzed Desymmetric Lactonization of Alkynylmalonic Acids Enabled by Chiral Bifunctional P,N ligands

et al. 2022

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“…Catalytic asymmetric hydrogenation of unsaturated carboxylic acids has been quite well explored, especially using noble metal catalysts, e.g., Rh catalyst, Ru catalyst, and Ir catalyst . All these research developments have been already documented well in various review articles; − therefore, these reports will be excluded here.…”

Section: Reaction Classificationmentioning

confidence: 99%

Carboxylic Acids as Building Blocks in Catalytic Asymmetric Reactions

Majumdar

2022

ACS Catal.

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Catalytic asymmetric transformation is a powerful strategy for the introduction of chirality to synthesize diverse nonracemic molecular entities. Chiral molecules play a significant role in the pharmaceutical area, as 50% of current drugs that are in use and 80% of the developing drugs are chiral. Asymmetric catalysis has been explored tremendously by synthetic organic chemists, and still continuous efforts are being directed toward advanced discoveries. The role of carboxylic acids as building blocks in catalytic asymmetric reactions is an emerging area. Carboxylic acids are known for their robustness and thus low reactivity. They are widely available, yet quite challenging substrates for catalytic asymmetric synthesis. The catalyst required for this kind of transformation must withstand acidic as well as oxidizing conditions. Catalyst and reaction design are required to break the glass ceiling of low reactivity of the acid substrates to ensure the useful transformation becomes successful. At the same time, high stereoselectivity needs to be achieved with complete control. Because of these challenges, carboxylic acids are highly intriguing substrates in the asymmetric catalysis research area, and more interesting methods are developing. There have been many important advancements in the last three decades. These literature reports show that carboxylic acids can act as both C- and O-nucleophiles. Furthermore, they can also be employed as electrophiles in asymmetric reactions under catalytic conditions. Brilliant application of catalyst and reaction designs made these transformations possible. This review article summarizes all these important developments on the use of carboxylic acids as building blocks in asymmetric catalysis.

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“…However, tetrasubstituted systems represent more challenging substrates where SIPHOX, SDP, or SFDP ligands clearly have their limitations. To overcome this issue, Chen and Zhang introduced in 2020 a series of O -SDP ligands which show a larger bite angle and higher electron density on the phosphorus atoms . Tetrasubstituted cyclic α,β-unsaturated carboxylic acids could be reduced with a Ru–- O -SDP complex in very high yield (up to 99%) and excellent enantioselectivity (up to 97%) as shown with a few selected examples in Scheme .…”

Section: Asymmetric Catalytic Reactions With Rigid C-stereogenic Spir...mentioning

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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Highly Enantioselective Hydrogenation of tetra - and tri -Substituted α,β-Unsaturated Carboxylic Acids with oxa -Spiro Diphosphine Ligands

Cited by 32 publications

References 57 publications

Gold‐Catalyzed Desymmetric Lactonization of Alkynylmalonic Acids Enabled by Chiral Bifunctional P,N ligands

Gold‐Catalyzed Desymmetric Lactonization of Alkynylmalonic Acids Enabled by Chiral Bifunctional P,N ligands

Carboxylic Acids as Building Blocks in Catalytic Asymmetric Reactions

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

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