Stereoselective Mannich Reaction of <i>N</i>‐(<i>tert</i>‐Butylsulfinyl)imines with 3‐Fluorooxindoles and Fluoroacetamides

Chen, Xiangyu; Li, Ya; Zhao, Jianbo; Zheng, Bu-quan; Lü, Qi; Ren, Xinfeng

doi:10.1002/adsc.201700353

Cited by 32 publications

(5 citation statements)

References 58 publications

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“…Imines 16 react with the enolate derived from fluoro indoles 52 to give the corresponding products 53 with excellent diastereoselectivities (Scheme 22). [41] The same process was also studied with fluoromethyl amide 54 to yield compounds 55 also with high diastereoselectivities. The stereochemistry observed could be explained through the transition states shown in Schemes 17 and 19, for compounds 53 and 55 , respectively.…”

Section: Organoalkaline Compoundsmentioning

confidence: 99%

Chiral N‐tert‐Butylsulfinyl Imines: New Discoveries

Foubelo

Yus

2020

The Chemical Record

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In this account the reactions of chiral N‐tert‐butylsulfinyl imines with organometallic reagents such as organoalkaline (lithium, sodium, potassium and cesium derivatives), organomagnesium, organozinc, organoboron, organoaluminium, organoindium and organosilicon compounds is comprehensively described. The reactivity in all cases is derived to synthetic applications in order to prepare interesting organic nitrogenated molecules, especially in the field of alkaloid compounds.

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Section: Organoalkaline Compoundsmentioning

confidence: 99%

Chiral N‐tert‐Butylsulfinyl Imines: New Discoveries

Foubelo

Yus

2020

The Chemical Record

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“…To our knowledge, although several papers have documented the catalytic asymmetric Michael addition between a nonfluorinated nucleophile and vinylidene bisphosphonate, studies on the use of 3-fluorooxindole as the Michael donor have not been disclosed. As a continuation of our interest in the functionalization of 3-fluorooxindoles, , we herein report a highly enantioselective Michael reaction of 3-fluorooxindoles and vinylidene bisphosphonates to synthesize 3-fluorooxindole scaffold-containing gem -BPs, using readily available bifunctional cinchona alkaloid organocatalysts.…”

Section: Introductionmentioning

confidence: 99%

Organocatalyzed Asymmetric Michael Addition of 3-Fluorooxindole to Vinylidene Bisphosphonates

Jin,

Wang,

Ning

et al. 2024

J. Org. Chem.

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Both the 3-fluorooxindole and germinal bisphosphonate structural motifs are prevalent in bioactive molecules because of their associated biological activities. We describe an approach to accessing 3,3-disubstituted 3-fluorooxindoles bearing a geminal bisphosphate fragment through a highly enantioselective Michael addition reaction between 3-fluorooxindoles and vinylidene bisphosphonates. These reactions are catalyzed by a commercially available cinchona alkaloid catalyst, have a broad substrate scope concerning 3-fluorooxindoles, and provide the corresponding addition products in a yield of up to 95% with an enantiomeric excess of up to 95%. A reasonable reaction pathway to explain the observed stereochemistry is also proposed.

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“…In many cases, the two bases are functionally interchangeable . In others, KHMDS offered inferior or superior yields, inferior or superior selectivities, superior yields at the expense of inferior selectivities, and vice versa . Of course, it is often unclear whether the results stem from the disilazide bases or from the resulting alkali-metal-salt intermediates.…”

Section: Introductionmentioning

confidence: 99%

Potassium Hexamethyldisilazide (KHMDS): Solvent-Dependent Solution Structures

Spivey,

Collum

2024

J. Am. Chem. Soc.

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Solution structures of potassium hexamethyldisilazide [KHMDS] and labeled [ 15 N]KHMDS were examined using a number of analytical methods including 29 Si NMR spectroscopy and density functional theory computations. A combination of 15 N− 29 Si couplings, 29 Si chemical shifts, and the method of continuous variations reveals dimers, monomers, and ion pairs. Weakly coordinating monofunctional ligands such as toluene, N,N-dimethylethylamine, and Et 3 N afford exclusively dimers. 1,3-Dioxolane, THF, dimethoxyethane, hexamethylphosphoramide, and diglyme provide dimers at low ligand concentrations and monomers at high ligand concentrations. N,N,N′,N'-Tetramethylethylenediamine and N,N,N′,N'-tetramethylcyclohexanediamine provide exclusively dimers at all ligand concentrations at ambient temperatures and significant monomer at −80 °C. Studies of 12-crown-4 ran into technical problems. Equimolar 15crown-5 forms a dimer, whereas excess 15-crown-5 affords a putative ion pair. Whereas equimolar 18-crown-6 also affords a dimer, an excess provides a monomer rather than a solvent-separated ion pair. [2.2.2]cryptand affords what is believed to be a contact-ionpaired cryptate. Solvation was probed using largely density functional theory (DFT) computations. Thermally corrected energies are consistent with lower aggregates and higher solvates at low temperatures, but the magnitudes of the computed temperature dependencies were substantially larger than the experimentally derived data.

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Stereoselective Mannich Reaction of N‐(tert‐Butylsulfinyl)imines with 3‐Fluorooxindoles and Fluoroacetamides

Cited by 32 publications

References 58 publications

Chiral N‐tert‐Butylsulfinyl Imines: New Discoveries

Chiral N‐tert‐Butylsulfinyl Imines: New Discoveries

Organocatalyzed Asymmetric Michael Addition of 3-Fluorooxindole to Vinylidene Bisphosphonates

Potassium Hexamethyldisilazide (KHMDS): Solvent-Dependent Solution Structures

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