1H, 13C, 17O and 33S NMR investigation of some cyclohexyl phenyl sulphides, sulphoxides and sulphones

Duddeck, H.; Korek, Uwe; Rosenbaum, Doris; Drabowicz, J.

doi:10.1002/mrc.1260240911

Cited by 29 publications

(6 citation statements)

References 44 publications

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“…[32] Axial S=O groups which are part of a sulfone moiety do not contribute to this effect and compounds bearing a sulfilimine group behave inconsistently in that context. [33] The 13 C shift of C-5 in monosulfone 10 is d = 16.5 ppm and is therefore comparable to the shift measured for trans-1,3-dithiane-1,3- Figure 5. Structure of sulfilimine 9 in the crystal.…”

Section: A Normal Perlin Effect Was Observed For Position C-5 a C H Tsupporting

confidence: 51%

Stereoelectronic Effects in Cyclic Sulfoxides, Sulfones, and Sulfilimines: Application of the Perlin Effect to Conformational Analysis

Wedel

Müller

Podlech

et al. 2007

Chemistry A European J

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The 1JC--H coupling constants in conformationally constrained sulfoxides, bissulfoxides, sulfoxide-sulfones, and sulfilimines derived from 2-benzylidene-1,3-dithiane and 2-(2,2-dimethylpropylidene)-1,3-dithiolane were measured by means of HMQC and HSQC NMR experiments and the Perlin effects were calculated. The type and the relative configuration of S==X groups (X= O, NTos) in these compounds have a strong influence on the magnitude of coupling constants for axial and equatorial C--H bonds, respectively. Axial S==O bonds give rise to a stereoelectronic effect on antiperiplanar axial C--H bonds. The resultant weakening of the respective C--H bonds leads to a smaller coupling constant than for a respective equatorial C--H bond. Equatorial S==O groups have an influence on beta-C--H bonds through a homoanomeric effect. Here, the axial C--H bond is weakened and a smaller coupling constant is measured. Sulfilimine groups show similar effects to sulfoxide groups.

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Section: A Normal Perlin Effect Was Observed For Position C-5 a C H Tsupporting

confidence: 51%

Stereoelectronic Effects in Cyclic Sulfoxides, Sulfones, and Sulfilimines: Application of the Perlin Effect to Conformational Analysis

Wedel

Müller

Podlech

et al. 2007

Chemistry A European J

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“…This results is an increase in electron density at the sulfinyl oxygen and, thus, in a reduction in the r À3 (Table 84). d( 17 O) for benzyl phenyl sulfoxide is À14 ppm, suggesting that non-bonding steric interactions, rather than resonance contributions, play a significant role [529]. 17 O NMR has been used to differentiate between diastereomeric [ 16 O, 17 O] sulfonyl oxygens in acyclic diastereomeric sulfoxides [534].…”

Section: Pomentioning

confidence: 99%

Oxygen-17 NMR spectroscopy: Basic principles and applications (Part I)

Gerothanassis

2010

Progress in Nuclear Magnetic Resonance Spectroscopy

126

107

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“…I and I1 are interconvertible via the pseudo rotation associated with S(1)-C(2)-C(3)-N (4) torsion. In 2 the best plane (in the X' sense) is defined by S ( l ) , C(2), N(4), C(5); the C(3) atom is displaced from this plane by 0.560 (7) A exo to the 40 46 4 c nucleus. Therefore, as can be seen in Fig.…”

Section: Description and Discussion Of The Crystal Strlictiirementioning

confidence: 99%

“…In the course of these comparative studies we became interested in introducing an oxygen atom at a specific site of the 6,6-dibromo3a-cyano-2,2-dimethylpenam (I). Of special interest was the stereocontrolled access to ( R ) -and (S)-sulfoxides of dibromo derivatives like 2 and 3, and also to their corresponding 6P-and 6a-bromo derivatives, to study the dependence of the 170 and, particularly, the 33S nmr parameters on the stereochemistry (7).…”

mentioning

confidence: 99%

Stereospecific synthesis, ¹H and ¹³C NMR spectroscopy, and X-ray crystallographic studies of 6,6-dibromo-3α-cyano-2,2-dimethylpenam-(1R)-S-oxide

Salomón¹,

Mascaretti²,

Strouse³

et al. 1991

Can. J. Chem.

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Can. J. Chem. 69,578 (1991). A stereospecific synthesis of 6,6-dibromo-3a-cyano-2,2-dimethylpenam-(1R)-S-oxide (2) is described. The X-ray single crystal investigation of this compound show! that it crystallizes in the mono~linic system, space group P 2 ' , with cell parameters a = 6.194(1), b = 9.363(1), c = 9.869(1) A, P = 96.55(2)", V = 568(1) A~, and two molecules per unit cell. The structure was solved, from low temperature data, by direct methods, and refined, by least-squares procedures, to a final R = 3.17%, R,,, = 3.38%, for 122 1 observe: independent reflections. The sulfoxide configuration is R. The thiazolidine presents an envelope shape with the C(3) atom 0.56 A above the other four members of the ring mean plane. Therefore, it exhibits the conformation with a-CH3 pseudoequatorial and P-CH3 and a-CN both pseudoaxial. This conformation is different from the one reported for other penicillin sulfoxide derivatives. The geometry of the p-lactam ring is typical of the fused bicyclic penam nucleus. The ring is non-planar. The N(4) atom displays a pyramidial arrangement. The examination of crystal packing shows that molecules along a are connected by a short C-H.. .O contact.Reported single crystal studies showed two dominant conformations for the thiazolidine ring in the fused bicyclic penam nucleus: the C(3) or 2P-3a substituents both pseudoaxial, as found in 2, and the S(1) or 2P-3a substituents both pseudoequatorial, adopted by most sulfoxides. Neither of these conformations can explain the nuclear Overhauser effect data. A conformation with the substituents C2-P-methylLC3-a-H and C2-a-methyl-C3-a-CN fully eclipsed is in accordance with the experimental results in the solution. The 'H nuclear magnetic resonance data reflect the influence of the magnetic anisotropy of the CN triple bond on the gemdimethyl groups, particularly in relation with the geometrical features of the molecule. Comparison of I3C nuclear magnetic resonance chemical shifts for 2 and its parent penicillin sulfide (1) indicates configurationally dependent substituent effects, the magnitude of which can be used for the stereochemical assignment of sulfoxide groups in this series.Key words: penicillin sulfoxide derivatives, di-halogen penicillanates, stereospecific synthesis, NMR studies, absolute configuration determination. CLAUDIO J. SALOMON, ORESTE A. MASCARETTI, CHARLES E. STROUSE et G. PUNTE. Can. J. Chem. 69,578 (1991). On dCcrit une synthkse stCrCosptcifique du 6,6-dibromo-3a-cyano-2,2-dimethylpenam-(1 R)-S-oxyde (2). Une etude par diffraction des rayons-X par un cristal unique de ce compose montre qu'il cristallise dans le systkme qonoclinique, groupe d'espace P 2 ) , avec a = 6,194(1), b = 9,363(L) et c = 9,869(1) A, P = 96,55(2)", Z = 2 et V = 568(1) A~. On a determine la structure par des mithodes directes a l'aide de donnees obtenues a basse temperature et on l'a affinee par la methode des moindres carrks (matrice complete) jusqu'i des valeurs de R = 0,0317 et R,,. = 0,0338 pour 1221 reflexions indipendantes. La confi~urat...

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¹H, ¹³C, ¹⁷O and ³³S NMR investigation of some cyclohexyl phenyl sulphides, sulphoxides and sulphones

Cited by 29 publications

References 44 publications

Stereoelectronic Effects in Cyclic Sulfoxides, Sulfones, and Sulfilimines: Application of the Perlin Effect to Conformational Analysis

Stereoelectronic Effects in Cyclic Sulfoxides, Sulfones, and Sulfilimines: Application of the Perlin Effect to Conformational Analysis

Oxygen-17 NMR spectroscopy: Basic principles and applications (Part I)

Stereospecific synthesis, ¹H and ¹³C NMR spectroscopy, and X-ray crystallographic studies of 6,6-dibromo-3α-cyano-2,2-dimethylpenam-(1R)-S-oxide

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1H, 13C, 17O and 33S NMR investigation of some cyclohexyl phenyl sulphides, sulphoxides and sulphones

Cited by 29 publications

References 44 publications

Stereoelectronic Effects in Cyclic Sulfoxides, Sulfones, and Sulfilimines: Application of the Perlin Effect to Conformational Analysis

Stereoelectronic Effects in Cyclic Sulfoxides, Sulfones, and Sulfilimines: Application of the Perlin Effect to Conformational Analysis

Oxygen-17 NMR spectroscopy: Basic principles and applications (Part I)

Stereospecific synthesis, 1H and 13C NMR spectroscopy, and X-ray crystallographic studies of 6,6-dibromo-3α-cyano-2,2-dimethylpenam-(1R)-S-oxide

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Product

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¹H, ¹³C, ¹⁷O and ³³S NMR investigation of some cyclohexyl phenyl sulphides, sulphoxides and sulphones

Stereospecific synthesis, ¹H and ¹³C NMR spectroscopy, and X-ray crystallographic studies of 6,6-dibromo-3α-cyano-2,2-dimethylpenam-(1R)-S-oxide