Synthesis and evaluation of C2-symmetric bis-sulfinamides as effective ligands in rhodium catalyzed addition of arylboronic acids to cycloalkenones

Revu, Omkar; Uphade, Manoj B.; Prasad, Kavirayani R.

doi:10.1016/j.tet.2016.07.024

Cited by 10 publications

(5 citation statements)

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“…Enantiopure sulfoxides, which are appreciated for their ease of synthesis and high stability, are important auxiliaries in asymmetric synthesis and excellent ligands for certain metal-catalyzed asymmetric organic transformations, in which the polarized R 2 + S–O – function appears to induce chirality also through electrostatic effects . Inspired by Knochel’s effective norbornene-derived sulfoxide-alkene 3 (see Table ) and highly flexible sulfinamido-alkene designs of type 4 and since our laboratory has been developing chiral P-alkene ligands such as 1 based on the dibenzo[ b , f ]azepine scaffold, we have been interested to extend this architecture to S(O)-dibenzazepinyl analogues by connecting the N atom with readily available chiral sulfinyl electrophiles. The alkene functions in ligands 1 – 4 are expected to be hemilabile thus enhancing catalyst performance.…”

Section: Introductionmentioning

confidence: 99%

Developing Chiral Dibenzazepine-Based S(O)-Alkene Hybrid Ligands for Rh(I) Complexation: Catalysts for the Base-Free Hayashi–Miyaura Reaction

et al. 2018

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A stereodivergent synthesis using inexpensive reagents, i.e., dibenzazepine and glucose-derived t-Bu-sulfinate diastereomers (R S )-6 or (S S )-6, affords respective S(O)-alkene hybrid ligands (S)-7 and (R)-7 on gram scales and in excellent optical purity (ee > 99%). Phenyl substitution of the dibenzoazepine backbone generates planar chirality to give epimerizationresistant (pS,R S )-10 diastereoisomer in high isomeric purity. Furthermore, the crystal structure of widely used sulfinate (R S )-6 is disclosed for the first time since its discovery a quarter of a century ago. Ligands 7 and 10 coordinate Rh(I) in a bidentate fashion through the S atoms and the alkene functions as evidenced by the crystal structures of complexes (R)-11 and (S N ,S S )-12. (R)-11 catalyzes the conjugate addition of arylboronic acids to enones with enantioselectivities of up to 77% ee. The reaction proceeds smoothly also under base-free conditions at 40 °C. The planar chirality in ligand (pS,R S )-10 is shown to override and invert the sense of chiral induction predicted by the configuration of the sulfur donor atom.

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Section: Introductionmentioning

confidence: 99%

Developing Chiral Dibenzazepine-Based S(O)-Alkene Hybrid Ligands for Rh(I) Complexation: Catalysts for the Base-Free Hayashi–Miyaura Reaction

et al. 2018

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“…All reactions were carried out under argon atmosphere. All glassware used was dried in electric oven at 120 o C. All new compounds were characterized by 1 H NMR, 13 C NMR, HR-MS and IR spectroscopy, unless otherwise mentioned. Nuclear magnetic resonance spectra were recorded on a 300MHz instrument or 400 MHz instrument.…”

Section: Methodsmentioning

confidence: 99%

“…All 1 H NMR experiments are reported in δ units, parts per million (ppm), and were measured relative to the signals for residual chloroform (7.26 ppm), DMSO (2.50 ppm) or acetone (2.05 ppm) in the deuterated solvent, unless otherwise stated. All 13 C NMR spectra are reported in ppm relative to deuterochloroform (77.2 ppm), DMSO-d 6 (39.5 ppm) or acetone-d 6 (206.7 ppm for C=O) unless otherwise stated, and all were obtained with 1 H decoupling. All IR spectra were taken on an infrared spectrometer.…”

Section: Methodsmentioning

confidence: 99%

“…The residual was purified with a silica gel column chromatography with a mixed solution of petroleum ether and ethyl acetate , 1H), 4.45 (ddd, J 16.8, 6.2, 1.5 Hz, 1H), 4.24 (ddd, J 16.8, 5.6, 1.5 Hz, 1H), 1.28 (d, J 11.9 Hz, 8H). 13 C for 3 h, the reaction mixture was then cooled to room temperature, quenched by water, and extracted with ethyl acetate (15 mL) for three times. The combined organic layer was dried over anhydrous MgSO4.…”

Section: Methodsmentioning

confidence: 99%

“…11 Recently chiral sulfoxide-and sulfinamide-olefins are developing as new types of chiral ligands. [12][13] Knochel, 14 Xu, [15][16][17] Du, [18][19] Liao, [20][21] Wan, 22 Chen, 23 Zeng 24 and so on have developed a series of chiral sulfoxide-olefin and sulfinamide-olefin ligands. Some typical chiral ligands are shown in Figure 1.…”

Section: Introductionmentioning

confidence: 99%

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Chiral N-aryl tert-butanesulfinamide-olefin ligands for rhodium-catalyzed asymmetric 1,4-addition of aryl boronic acids to cyclic enones

Yuan¹,

Zeng²,

Wang³

et al. 2017

Arkivoc

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Chiral N-aryl sulfinamide-olefins which are readily synthesized via C-N coupling and nucleophilic substitution have been used as chiral ligands, which demonstrate moderate to excellent asymmetric catalytic performance in the rhodium-catalyzed asymmetric 1,4-addition of aryl boronic acids to cyclic enones. The chiral ligands are readily synthesized via C-N coupling reaction and nucleophilic substitution. Given that chiral ligands with 97%ee produced 1,4-addition products up to 95%ee, N-aryl tert-butanesulfinamide-olefin ligands demonstrates fairly high chiral induction ability in the rhodium-catalyzed asymmetric 1,4-addition.

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Enantioselective, Rhodium‐Catalyzed 1,4‐Addition of Organoboron Reagents to Electron‐Deficient Alkenes

2017

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The rhodium‐catalyzed 1,4‐addition of organoboron reagents to electron‐deficient alkenes is a versatile method for the enantioselective construction of carbon–carbon bonds. The scope of these reactions is broad, and alkenes activated by adjacent carbonyls, imines, nitriles, phosphonyl groups, nitro groups, sulfonyl groups, C=N‐containing aromatic heterocycles, electron‐deficient arenes, or boryl groups are effective substrates. Regarding the pronucleophilic component, aryl‐, heteroaryl‐, and alkenylboron reagents have been successfully employed. In addition, numerous chiral ligands have been developed which impart high enantioselectivities onto these reactions. Importantly, these reactions usually proceed under mild, experimentally convenient conditions, with no requirement for precautions to exclude air or moisture. This chapter presents the scope and limitations of this process, along with a discussion of the current understanding of the mechanistic and stereochemical features. Incorporation of this process into domino reactions is discussed, as is its application in the synthesis of biologically active molecules. The literature is covered up until the end of 2013.

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Synthesis and evaluation of C2-symmetric bis-sulfinamides as effective ligands in rhodium catalyzed addition of arylboronic acids to cycloalkenones

Cited by 10 publications

References 5 publications

Developing Chiral Dibenzazepine-Based S(O)-Alkene Hybrid Ligands for Rh(I) Complexation: Catalysts for the Base-Free Hayashi–Miyaura Reaction

Developing Chiral Dibenzazepine-Based S(O)-Alkene Hybrid Ligands for Rh(I) Complexation: Catalysts for the Base-Free Hayashi–Miyaura Reaction

Chiral N-aryl tert-butanesulfinamide-olefin ligands for rhodium-catalyzed asymmetric 1,4-addition of aryl boronic acids to cyclic enones

Enantioselective, Rhodium‐Catalyzed 1,4‐Addition of Organoboron Reagents to Electron‐Deficient Alkenes

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