Selectivity in the free-radical reduction of lactones with trichlorosilane

Bladwin, S. W.; Doll, Ronald J.; Haut, Stephen A.

doi:10.1021/jo00930a053

Cited by 16 publications

(7 citation statements)

References 2 publications

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“…60XA-d2 was prepared by a modification of a published procedure (17). A solution of the lactone (24 mmol) in ether (50 mL) was added dropwise to a stirred slurry of LiAlD, (38 mmol) in ether (90 mL).…”

Section: -Oxabicyclo[32 I]octane (60xa)mentioning

confidence: 99%

The vibrational spectra (100–1500 cm⁻¹) of a series of bicyclo[3.2.1]octanes assigned by means of scaled 3-21G ab initio harmonic force fields

Eggimann¹,

Ibrahim²,

Shaw³

et al. 1993

Can. J. Chem.

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The infrared absorption (vapor phase and solution) and Raman (liquid phase) spectra of bicyclo[3.2.1]octane, 8-oxabicyclo[3.2.1]octane, 6-oxabicyclo[3.2.1]octane, 6,8-dioxabicyclo[3.2.1]octane, and the 7,7-dideutero-substituted derivatives of the last two compounds are reported in the region 100–1500 cm−1 for the first time. The vibrational spectra are assigned almost completely with the guidance of ab initio 3-21G geometries and scaled force fields. A total of 14 force-field scale facors are transferred from smaller molecules, predicting the frequencies with an average error of 7.6 cm−1 (1.2%) for 196 assigned transitions. After optimizing the factors in an overlay refinement involving all six molecules, the frequencies are within 5.7 cm−1 (0.75%) of experiment. The ab initio absorption and Raman intensities are calculated with the 3-21G basis set and are demonstrated to be of such accuracy as to be useful for the spectral assignments. These intensities are calculated with uniformly and nonuniformly scaled force fields and compared to the experimental spectra. The intensities derived from the latter force fields are superior, meaning that nonuniform scaling is preferable at this level of theory for both vibrational frequencies and normal mode descriptions.

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Section: -Oxabicyclo[32 I]octane (60xa)mentioning

confidence: 99%

The vibrational spectra (100–1500 cm⁻¹) of a series of bicyclo[3.2.1]octanes assigned by means of scaled 3-21G ab initio harmonic force fields

Eggimann¹,

Ibrahim²,

Shaw³

et al. 1993

Can. J. Chem.

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“…We have prepared them by standard (Williamson) methods and report pertinent physical data below. Dodecyl Ethyl Ether (5): bp 97°( 1.25 mm, Kugelrohr); NMR (CCD a 0.89 (t, J = 6 Hz, 3 H, -CH3), 1.15 (t, J = 7.5 Hz, 3 H, -CH3), 1.29 (broad s, 20 H, -CH2-), 3.35 (q, J = 6 Hz, 2 H, -CH20-), 3.39 (q, J = 7.5 Hz, 2 H, -OCH2-).…”

Section: Methodsmentioning

confidence: 99%

“…[lit.16 117-119°(3 mm)]; NMR (CC14) 5 1.12 (t, J = 7 Hz, 3 H, -CH3), 1.36 (broad s, 22 H, -CH2-), 3.32 (m, unresolved, 1 H, CHO-), 3.36 (q, J = 7 Hz, 2 H, -OCH2-).…”

Section: Methodsmentioning

confidence: 99%

“…strated the applicability of the reagent to the reduction of more complex bicyclic lactones and also the existence of significant selectivity when additional ester groupings were present. 3 We now wish to report that under the appropriate conditions trichlorosilane can be an effective reagent for the reductive deoxygenation of esters of nonprimary aliphatic alcohols. In general we find that for the reaction of a given ester 1 with trichlorosilane, two products, 2 and 3, are formed competitively.…”

mentioning

confidence: 99%

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Reductive deoxygenation of esters with trichlorosilane

Baldwin¹,

Haut²

1975

J. Org. Chem.

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“…Among the reaction products, 3-methoxycyclohexanol, 24 2-methoxy-2-methylcyclohexanol, 25 3-methoxy-3-methylcyclohexanol, 25 3-methoxy-3,5-dimethylcyclohexanol, 25 3methoxycyclopentanol, 26 (3-methoxycyclohexane)methanol, 27 6-oxabicyclo[3.2.1]octane, 28 1-methyl-…”

Section: Productsmentioning

confidence: 99%

Regio- and stereoselectivity in the solvomercuriation and intramolecular alkoxymercuriation of cyclic unsaturated alcohols

Senda

Takayanagi

Sudo

2001

J. Chem. Soc., Perkin Trans. 1

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Selectivity in the free-radical reduction of lactones with trichlorosilane

Cited by 16 publications

References 2 publications

The vibrational spectra (100–1500 cm⁻¹) of a series of bicyclo[3.2.1]octanes assigned by means of scaled 3-21G ab initio harmonic force fields

The vibrational spectra (100–1500 cm⁻¹) of a series of bicyclo[3.2.1]octanes assigned by means of scaled 3-21G ab initio harmonic force fields

Reductive deoxygenation of esters with trichlorosilane

Regio- and stereoselectivity in the solvomercuriation and intramolecular alkoxymercuriation of cyclic unsaturated alcohols

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Selectivity in the free-radical reduction of lactones with trichlorosilane

Cited by 16 publications

References 2 publications

The vibrational spectra (100–1500 cm−1) of a series of bicyclo[3.2.1]octanes assigned by means of scaled 3-21G ab initio harmonic force fields

The vibrational spectra (100–1500 cm−1) of a series of bicyclo[3.2.1]octanes assigned by means of scaled 3-21G ab initio harmonic force fields

Reductive deoxygenation of esters with trichlorosilane

Regio- and stereoselectivity in the solvomercuriation and intramolecular alkoxymercuriation of cyclic unsaturated alcohols

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Product

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The vibrational spectra (100–1500 cm⁻¹) of a series of bicyclo[3.2.1]octanes assigned by means of scaled 3-21G ab initio harmonic force fields

The vibrational spectra (100–1500 cm⁻¹) of a series of bicyclo[3.2.1]octanes assigned by means of scaled 3-21G ab initio harmonic force fields