Selective Synthesis of C1-Symmetric BINOL-phosphates and P-chiral Phosphoramides Using Directed ortho-Lithiation

Volpe, Rohan; Law, Hanson Y.-L.; White, Jonathan M.; Flynn, Bernard L.

doi:10.1021/acs.orglett.1c02430

Cited by 8 publications

(11 citation statements)

References 32 publications

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“…Therefore, this is not a diastereoselective reaction. 16 The optical purity in this case is based on axial chirality. When subjected to various aryl boronic acids, R-3 yielded aryl ketones R-4b−d and R-4g−i in moderate to very good yields without losing optical purity (Table 3).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Nickel Catalyzed Selective Arylation of Geminal Dinitriles: Direct Access to α-Cyano Carbonyl Compounds

Bhattacharya,

Subramaniam,

Kandukuri

et al. 2024

J. Org. Chem.

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The catalytic intermolecular arylation of disubstituted geminal dinitriles with in situ generated arylnickel complexes is disclosed. This method efficiently provides various all-carbon substituted α-cyanocarbonyl compounds without additives and an inert atmosphere. It also demonstrates the arylation of R-BINOL and S-BINOL derived geminal dinitriles, preserving optical purity. Mechanistic studies proved that the in situ generated organonickel complex is involved in arylation.

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Section: ■ Results and Discussionmentioning

confidence: 99%

“…The apparent diastereomers, such as R -axial/ R and R -axial/ S , are actually identical, as they can be interconverted by a 180° rotation. Therefore, this is not a diastereoselective reaction . The optical purity in this case is based on axial chirality.…”

Section: Results and Discussionmentioning

confidence: 99%

Nickel Catalyzed Selective Arylation of Geminal Dinitriles: Direct Access to α-Cyano Carbonyl Compounds

Bhattacharya,

Subramaniam,

Kandukuri

et al. 2024

J. Org. Chem.

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“…When ( S )-BINOL-phosphoric acid ( S )- 311 was treated with 3.1 equiv of s BuLi in THF at −78 °C for 1.5 h followed by addition of 1,2-diiodoethane, the 3,3′-diiodo product ( S )- 312 was obtained in 80% yield (Scheme ). The monoiodo product ( S )- 313 was obtained in 68% yield from the reaction of ( S )- 311 with 3.4 equiv of n BuLi and TMEDA in THF at −78 °C to −40 °C for 2 h, followed by the addition of I 2 . Monoiodonation of the monophenyl compound ( S )- 314 gave the unsymmetrically disubstituted compound ( S )- 315 in 41% yield (Scheme ).…”

Section: Ortho-lithiation At 3-positionmentioning

confidence: 99%

Regioselective Substitution of BINOL

2024

Chem. Rev.

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1,1′-Bi-2-naphthol (BINOL) has been extensively used as the chirality source in the fields of molecular recognition, asymmetric synthesis, and materials science. The direct electrophilic substitution at the aromatic rings of the optically active BINOL has been developed as one of the most convenient strategies to structurally modify BINOL for diverse applications. High regioselectivity has been achieved for the reaction of BINOL with electrophiles. Depending upon the reaction conditions and substitution patterns, various functional groups can be introduced to the specific positions, such as the 6-, 5-, 4-, and 3-positions, of BINOL. Ortho-lithiation at the 3-position directed by the functional groups at the 2-position of BINOL have been extensively used to prepare the 3- and 3,3′-substituted BINOLs. The use of transition metal-catalyzed C–H activation has also been explored to functionalize BINOL at the 3-, 4-, 5-, 6-, and 7-positions. These regioselective substitutions of BINOL have allowed the construction of tremendous amount of BINOL derivatives with fascinating structures and properties as reviewed in this article. Examples for the applications of the optically active BINOLs with varying substitutions in asymmetric catalysis, molecular recognition, chiral sensing and materials are also provided.

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“…Although P‐based DMGs have been comparatively less studied, a number of phosphorus‐centered directing groups containing a P=X moiety (X=C, N, O, S) have proven their effectiveness in ortho ‐C−H functionalization processes via DoLi [7] . These include phosphoranes, [8] phosphazenes, [9] phosphine oxides, [8a,10] phosphinic acids, [11] phosphinic amides, [12] phosphinothioic amides, [13] phosphinimidic amides, [14] phosphonates, [15] phosphonic amides, [16] phosphonamidates, [17] phosphonothioic diamides, [18] phosphoramides [19] and phosphorodiamides [20] . The applications of the ortho ‐lithiated species as building blocks in organic synthesis are greatly enhanced by their behavior as bidentate and tridentate ligands very useful for the preparation of main group, transition metal and rare earth complexes via methatetic reactions [21] including the synthesis of P‐stereogenic derivatives [14a,19,22] …”

Section: Introductionmentioning

confidence: 99%

Crystal, Solution, and Computational Study of the Structure of Ortho‐Lithium N,N‐Diisopropyl‐P,P‐Diphenylphosphinothioic Amide

Belmonte‐Sánchez,

García‐López,

Navarro

et al. 2024

Chemistry A European J

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The first crystal structure of an ortho‐lithium phosphinothioic amide complexed with tetramethylethylenediamine 12 is reported. The complex consists of a spirane in which the spirolithium is N,N‐ and C,S‐chelated by the diamine and organophosphorus ligands, respectively. The analogous ortho anion 14 obtained by Sn(IV)/Li transmetallation in THF has also been synthesized. Nuclear magnetic resonance study of both anions showed that they exist as monomers in solution and are involved in dynamic processes including the restricted rotation around the P‒N bond. 14 is converted at room temperature by nucleophilic cyclization to the dearomatized anion 15, which evolves after a few hours to the benzophosphindole sulfide 16. Density functional theory calculations supported the aggregation state in solution and were used to explore the conformational space of anion 12, the mechanism of ortholithiation directed by P(X)‐N (X = O, S) groups, and the mechanism of formation of 15.

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Selective Synthesis of C₁-Symmetric BINOL-phosphates and P-chiral Phosphoramides Using Directed ortho-Lithiation

Abstract: Method of preparation of all new compounds and copies of their 1 H and 13 C NMR spectra (PDF)Accession Codes CCDC 2093578 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk

Cited by 8 publications

References 32 publications

Nickel Catalyzed Selective Arylation of Geminal Dinitriles: Direct Access to α-Cyano Carbonyl Compounds

Nickel Catalyzed Selective Arylation of Geminal Dinitriles: Direct Access to α-Cyano Carbonyl Compounds

Regioselective Substitution of BINOL

Crystal, Solution, and Computational Study of the Structure of Ortho‐Lithium N,N‐Diisopropyl‐P,P‐Diphenylphosphinothioic Amide

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