Sulfur-carbon-phosphorus anomeric interactions. 5. Conformational preference of the diphenylthiophosphinoyl group [(C6H5)2P(S)] in cyclohexane and in the 1,3-dithian-2-yl ring

Juaristi, Eusebio; Lopez-Nunez, Norma A.; Valenzuela, Bertha A.; Valle, Lucia; Toscano, Rubén A.; Soriano-Garcı́a, Manuel

doi:10.1021/jo00232a023

Cited by 20 publications

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“…Methyl diphenylphosphinothioite ( 19 ), cis -5- tert -butyl-2-(diphenylthiophosphinoyl)-1,3-dithiane ( 30a ), − trans -5- tert -butyl-2-(diphenylthiophosphinoyl)-1,3-dithiane ( 30e ), − r -2-(diphenylthiophosphinoyl)- t -4, t -6-dimethyl-1,3-dithiane ( 31a ), − r -2-(diphenylthiophosphinoyl)- t -4, t -6-dimethyl-1,3-dithiane ( 31e ), − 5- tert -butyl-1,3-dithiane ( 32 ), ,, and cis -4,6-dimethyl-1,3-dithiane ( 33 ) 67,69,70 were prepared acccording to known procedures. Other compounds if not described below were commercially available.…”

Section: Methodsmentioning

confidence: 99%

Inapplicability of the Antiperiplanar Lone Pair Hypothesis to C−P Bond Breaking and Formation in Some S−C−P⁺Systems

Graczyk¹,

Mikołajczyk²

1996

J. Org. Chem.

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Both C(2)-P bond breaking and formation in the S-C-P(+) system do not occur according to the antiperiplanar lone pair hypothesis. Experiments using 2-phosphonio derivatives of 5-tert-butyl-1,3-dithiane and cis-4,6-dimethyl-1,3-dithiane are against the participation of higher-energy boat conformers as reactive intermediates. The results obtained support a possibility of conformational adjustment in the course of the reaction. Stereoelectronic control of the C(2)-P bond breaking and formation results from interplay of several factors. The role of the n(S)-sigma(C(2))(-)(P) and sigma(C(4,6))(-)(S)-sigma(C(2))(-)(P) hyperconjugation, as well as of the repulsive interactions between lone electron pairs pi(S) of endocyclic sulfur atoms and pi-electrons of the phenyl ring(s) connected with phosphorus, is discussed.

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Section: Methodsmentioning

confidence: 99%

Inapplicability of the Antiperiplanar Lone Pair Hypothesis to C−P Bond Breaking and Formation in Some S−C−P⁺Systems

Graczyk¹,

Mikołajczyk²

1996

J. Org. Chem.

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“…Crystallization from n-hexane gave analytically pure sample as needles: mp 103.4-104.2 °C; NMR (300.13 MHz, CDC13) 0.92 (s, 9H, CH3C), 1.69 (tt, Vh-h = 11.54 Hz, VH-h = 2. 37 Hz, 1H, t-BuCff), 2.59 (dd, Vh-h = 13. 77 Hz, VH-h = 2.…”

Section: Methodsmentioning

confidence: 99%

“…77 Hz, VH-h = 2. 37 Hz, 2H, H(4,6)«,), 3.38 (ddd, VH-h = 13.77 Hz, VH-h = 11.54 Hz, VH-p = 1.65 Hz,2H,H(4,6)ti), 3.42 (d, Vh-p = 18.0 Hz, 1H, HCP), 3.90 (d, VH-p = 10.56 Hz, 6H, CH30); 31P NMR (121.49 MHz, CDClg) 21.3; 13C NMR (75.47 MHz, CDClg) 27.04 (s, CH2), 27.13 (s,CHgC),31.76 (d, Vc-p = 159.5 Hz, CHP), 34.12 (s, CMe3), 46.44 (d, Vc-P = 1.8 Hz, CHt-Bu), 54.51 (d, Vc-p = 7.4 Hz, CHgO); IR (KBr) 1020 (vs), 1059 (vs), 1222 (vs) cm-1; MS (70 eV) m/e (relative intensity) 284 (20, M*+), 175 (100), 147 (16), 57 (34), 45 (17), 41 (28). Anal.…”

Section: Methodsmentioning

confidence: 99%

“…5,]-l,3dithiane (lib). Following the general procedure of Juaristi et al,37 dithiane 32 (2.96 g, 20.0 mmol) and chlorophosphine 33 (3.80 g, 24.0 mmol) were converted into a mixture which, after chromatographic separation on silica gel with benzene-acetone as an eluent and subsequent crystallization from ethyl acetate, afforded lib (3.19 g, 52.7%), colorless crystals: mp 126.2-128.0 °C; NMR (300.13 MHz, CD2C12) 1.09 (s, 3H, CHgC), 1.14 (s, 3H, CHgC), 2.17 (d, VH-P = 12.7 Hz, 3H, CH3P), 2.37 (d, VH.H = 13.8 Hz, 1H, C'HH), 2.45 (d, VH-H = 13.8 Hz, 1H, C"fíH), 3.04 (dd, Vh-h = 13.8 Hz, VH-P = 3.0 Hz, 2H, C'HH), 3.10 c/s-5-tert-Butyl-2-[methylphenyl(thiopho8phinoyl)]-l,3dithiane (11c). The reaction was carried out in an atmosphere of dry nitrogen.…”

Section: Methodsmentioning

confidence: 99%

“…Found: C, 51.79; H, 6.49. jr-2-[Methylphenyl(thiophosphinoyl)]-c-4,c-6-dimethyl-1,3-dithiane (Ilf). Following the general procedure of Juaristi et al,37 dithiane 15 (2.96 g, 20.0 mmol) and chlorophosphine 33 (3.80 g, 24.0 mmol) were converted into a mixture which, after chromatographic separation on silica gel with benzene-acetone as an eluent and subsequent crystallization from chloroformdiethyl ether, afforded Ilf (2.647 g, 43.8%), colorless crystals: mp 124.5-130.0 °C; NMR (300.13 MHz, CD2C12) 1.23 (dd, Vh-h = 6.8 Hz, VH-P = 0.4 Hz, 3H, CHgC'), 1.23 (dt, Hz, Vh-h = 11.50 Hz, 1H, ( 5) ), 1.25 (dd, VH-H = 6.8 Hz, VH-P = 0.4 Hz, 3H, CHgC"), 2.08 (ddt, VH-h = 14.0 Hz, VH-p = 4.2 Hz, Vh-h = 2.29 Hz, 1H, H(5)«,), 2.18 (d, VH-P = 13.1 Hz, 3H, CHgP), 2.88 (dqdd, VH-h = 11.50 Hz, VH-H = 6.8 Hz, VH-h = 2. 29 Hz, Vh-p = 1.0 Hz, 1H, Ctf'CHg), 2.91 (dqdd, VH-h = 11.50 Hz, VH-H = 6.8 Hz, Vh-h = 2.…”

Section: Methodsmentioning

confidence: 99%

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Conformational Preference in 1,3-Dithianes Containing 2-Phosphoryl, -(thiophosphoryl), and -(selenophosphoryl) groups. Chemical and Crystallographic Implications of the Nature of the Anomeric Effect

Mikołajczyk¹,

Graczyk²,

Wieczorek³

1994

J. Org. Chem.

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The operation of the anomeric effect in all the title compounds studied was found. The magnitude of the anomeric effect was found to be larger than 10 kJ/mol. Crystallographic, spectroscopic, and thermodynamic data suggest that the ns~ff*c-P hyperconjugative interaction is one of the factors responsible for the anomeric effect. The second interaction stabilizing the axial position of phosphorus can be P=Y-H(4 or 6) hydrogen bond formation. Some other interactions are also possible, namely ffC(4,6)-s-ff*C(2)~p (preferring the equatorial position of phosphorus) and < 4,6)-8"""•* -y hyperconjugations and the nsrepulsions. The latter interaction was also proposed as MO counterpart of lone pair-lone pair repulsions suggested by molecular mechanics calculations. It was proved that various conformation probes can afford different equilibrium constants, if weighted average method and conformationally fixed models are applied. Most of the physical quantities are dependent on the alkyl substitution in the 1,3-dithiane ring. Thus, the relevant procedure for the selection of conformational probe was presented. Since the -effect value in 13C NMR spectra was found to be very sensitive to the position of a substituent connected with the anomeric carbon atom of 1,3dithianes, it was applied as a conformational probe. A long range 4 5Jc-p coupling constant in the 13C NMR spectra and 31P spin-lattice TiDD relaxation times suggest the existence of close contact(s) between a heteroatom Y (Y = O, S, Se) connected with the axial phosphorus P=Y and axial protons H(4,6) in the 1,3-dithiane ring. Crystallographic data show that the distance from Y to one of these protons is usually much smaller than to the other one and smaller than the sum of H,Y van der Waals radii. The possibility of H-Y hydrogen bond formation is discussed.

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The conformational analysis of sulphur‐containing rings

Riddell

1993

PATAI'S Chemistry of Functional Groups

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Sulfur-carbon-phosphorus anomeric interactions. 5. Conformational preference of the diphenylthiophosphinoyl group [(C6H5)2P(S)] in cyclohexane and in the 1,3-dithian-2-yl ring

Cited by 20 publications

References 0 publications

Inapplicability of the Antiperiplanar Lone Pair Hypothesis to C−P Bond Breaking and Formation in Some S−C−P⁺Systems

Inapplicability of the Antiperiplanar Lone Pair Hypothesis to C−P Bond Breaking and Formation in Some S−C−P⁺Systems

Conformational Preference in 1,3-Dithianes Containing 2-Phosphoryl, -(thiophosphoryl), and -(selenophosphoryl) groups. Chemical and Crystallographic Implications of the Nature of the Anomeric Effect

The conformational analysis of sulphur‐containing rings

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Sulfur-carbon-phosphorus anomeric interactions. 5. Conformational preference of the diphenylthiophosphinoyl group [(C6H5)2P(S)] in cyclohexane and in the 1,3-dithian-2-yl ring

Cited by 20 publications

References 0 publications

Inapplicability of the Antiperiplanar Lone Pair Hypothesis to C−P Bond Breaking and Formation in Some S−C−P+Systems

Inapplicability of the Antiperiplanar Lone Pair Hypothesis to C−P Bond Breaking and Formation in Some S−C−P+Systems

Conformational Preference in 1,3-Dithianes Containing 2-Phosphoryl, -(thiophosphoryl), and -(selenophosphoryl) groups. Chemical and Crystallographic Implications of the Nature of the Anomeric Effect

The conformational analysis of sulphur‐containing rings

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Inapplicability of the Antiperiplanar Lone Pair Hypothesis to C−P Bond Breaking and Formation in Some S−C−P⁺Systems

Inapplicability of the Antiperiplanar Lone Pair Hypothesis to C−P Bond Breaking and Formation in Some S−C−P⁺Systems