Thermal racemization of diaryl, alkyl aryl, and dialkyl sulfoxides by pyramidal inversion

Rayner, Dennis R.; Gordon, Arnold J.; Mislow, Kurt

doi:10.1021/ja01020a019

Cited by 139 publications

(80 citation statements)

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“…Chiral tert-butanesulfinyl compounds have several advantages: practical and concise synthesis; 3,4,7,8 ortho-lithiation properties; 11 high stereogenic stabilities; 12 effective coordination capability with transition metals and excellent asymmetric inductions. 5,7,8 Recently, we focused our attention on transition-metal-catalyzed asymmetric reactions using chiral sulfoxide (tert-butanesulfinyl) ligands.…”

Section: Introductionmentioning

confidence: 99%

tert-Butanesulfinylthioether ligands: synthesis and application in palladium-catalyzed asymmetric allylic alkylation

Liu

Chen

Xing

et al. 2011

Tetrahedron: Asymmetry

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Section: Introductionmentioning

confidence: 99%

tert-Butanesulfinylthioether ligands: synthesis and application in palladium-catalyzed asymmetric allylic alkylation

Liu

Chen

Xing

et al. 2011

Tetrahedron: Asymmetry

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“…Thus, a sulfoxide with different carbon substituents is a stereogenic center. The ease of preparation [2][3][4] and stability 5 of optically active sulfoxides has made them very attractive as chiral auxiliaries for organic synthesis. [6][7][8][9][10][11] The fact that the pyramidal structure of sulfoxides retains its configurational integrity has generated considerable curiosity in understanding the conditions under which epimerization can occur.…”

Section: Introductionmentioning

confidence: 99%

Computational Studies of the Ground and Excited State Potentials of DMSO and H₂SO: Relevance to Photostereomutation

Cubbage

Jenks

2001

J. Phys. Chem. A

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A computational study on ground and excited states of dimethyl sulfoxide (DMSO) and the hypothetical molecule H 2 SO is reported. Full valence CASSCF/6-311+G(3df,2p) with a multireference perturbation theory correction was used for the latter, while DMSO was examined with an active space that neglected only the CH bonds and an analogous basis set that neglected polarization functions on H. A realistic value of 41.5 kcal/mol was obtained for the ground state pyramidal inversion of sulfur for DMSO, though no directly comparable experimental value is available. Calculations were also carried out on singlet and triplet excited state surfaces of both A′ and A′′ symmetry. Relaxed excited state geometries fairly near the ground state geometry were found, but perhaps more importantly, excited state stationary points were also found in C 2V symmetry. These were the lowest energy of any geometry on their respective surfaces. This leads to the speculation that photochemical stereomutation of alkyl sulfoxides may occur without C-S bond cleavage in a mechanism formally analogous to the photochemical cis-trans isomerization of olefins.

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“…For reference, the a 1 D state of SO, which contains a r and a p bond, is bound by 103.2 kcal/ mol. The transition state for inversion is 40.1 kcal/mol higher in energy than the minimum-similar to many other XYSO molecules where X and Y are not bonded together via rings [2,[53][54][55][56][57]. The equilibrium geometry of Cl 2 SO leads to two questions.…”

Section: The CL 2 So Isomermentioning

confidence: 94%

The nature of the SO bond of chlorinated sulfur–oxygen compounds

Lindquist

Dunning

2014

Theor Chem Acc

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Sulfur-oxygen chemistry encompasses a rich variety of chemical species and reactions. Sulfur-oxygen bonds can be quite short and strong, and historically, there has been disagreement as to the nature of the SO bond in sulfinyl groups. Early work invoked participation by the 3d orbitals of sulfur to explain the apparent double-bond character of sulfinyl bonds, but modern calculations have clearly established that sulfur 3d atomic orbitals do not participate as valence orbitals in hypervalent sulfur compounds. In prior work, we used generalized valence bond (GVB) theory to explain the features of the SO bond in the HSO/SOH structural isomers, and we extend that work here to the chlorinated analogs (ClSO/SOCl). We also use GVB theory to elucidate the nature of the bonding in Cl 2 SO and its higher energy structural isomer ClSOCl. We find that recoupled pair bonding, which we first introduced in our study of sulfur fluorides, is integral to describing the SO bond in all of these species. We also connect our analysis to the use of hyperconjugation to explain the backbonding in the p system in the sulfinyl halides.

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Thermal racemization of diaryl, alkyl aryl, and dialkyl sulfoxides by pyramidal inversion

Cited by 139 publications

References 2 publications

tert-Butanesulfinylthioether ligands: synthesis and application in palladium-catalyzed asymmetric allylic alkylation

tert-Butanesulfinylthioether ligands: synthesis and application in palladium-catalyzed asymmetric allylic alkylation

Computational Studies of the Ground and Excited State Potentials of DMSO and H₂SO: Relevance to Photostereomutation

The nature of the SO bond of chlorinated sulfur–oxygen compounds

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Thermal racemization of diaryl, alkyl aryl, and dialkyl sulfoxides by pyramidal inversion

Cited by 139 publications

References 2 publications

tert-Butanesulfinylthioether ligands: synthesis and application in palladium-catalyzed asymmetric allylic alkylation

tert-Butanesulfinylthioether ligands: synthesis and application in palladium-catalyzed asymmetric allylic alkylation

Computational Studies of the Ground and Excited State Potentials of DMSO and H2SO: Relevance to Photostereomutation

The nature of the SO bond of chlorinated sulfur–oxygen compounds

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Product

Resources

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Computational Studies of the Ground and Excited State Potentials of DMSO and H₂SO: Relevance to Photostereomutation