Barriers to intramolecular hydride transfers in some polycyclic hydroxyketones

Craze, Gabrielle-Anne; Watt, I. C.

doi:10.1039/p29810000175

Cited by 40 publications

(19 citation statements)

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“…The 13 C NMR spectrum of the minor component in CD 3 2 SO solution exhibits a resonance signal at 164.14 ppm which is characteristic 9 for the signal from a C(OR) N carbon atom, as manifested in a lactim functional group. The minor component should therefore probably be the lactim 4 (or 5).…”

Section: Resultsmentioning

confidence: 98%

“…Evidence that C-11 in 8 is coupled to two deuterium-exchangeable proton bearing atoms was obtained from a proton noise decoupled 13 C NMR spectrum recorded in CD 3 The structure of the triacetate 7 was also elucidated from a 1 H and 13 C NMR investigation. The 1 H NMR spectrum of 7 exhibits only one deuterium-exchangeable proton resonance at υ H D 8.551.…”

Section: Resultsmentioning

confidence: 99%

“…The mixture was evaporated to dryness and the product (2, Tables 3 and 4 for the NMR data for 6. A solution of 2 (0.5 g) in anhydrous 1,4-dioxane 20 cm 3 was cooled in an ice-bath and acetyl chloride 0.3 cm 3 and N,N-dimethylaniline 0.6 cm 3 were added simultaneously dropwise to the reaction mixture. 6 The reaction mixture was stirred for 10 min with cooling and then refluxed for 1 h, cooled and diluted with water 50 cm 3 …”

Section: Methodsmentioning

confidence: 99%

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Structure elucidation of 11‐amino‐8‐hydroxypentacyclo[5.4.0.0^{2, 6}.0^{3, 10}.0^{5, 9}]undecane‐8,11‐lactam through selective acetylation and complete ¹H and ¹³C NMR spectral assignment of the mono‐, di‐ and triacetates

Martins

Viljoen

Kruger

et al. 2004

Magnetic Reson in Chemistry

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NMR techniques cannot unambiguously distinguish between 11-amino-8-hydroxypentacyclo[5.4.0.0(2, 6).0(3, 10).0(5, 9)]undecane-8,11-lactam and 8-amino-11-hydroxypentacyclo[5.4.0.0(2, 6).0(3, 10).0(5, 9)]undecane-8,11-lactam, both of which are possible products during the reaction of pentacyclo[5.4.0.0(2, 6).0(3, 10).0(5, 9)]undecane-8,11-dione with Strecker reagents. Treatment of 11-amino-8-hydroxy-pentacyclo[5.4.0.0(2, 6).0(3, 10).0(5, 9)]undecane-8,11-lactam with acetic anhydride at room temperature produced a monoacetate. With acetic anhydride containing sodium acetate, a triacetate was obtained at reflux temperature. Treatment with acetyl chloride and N,N-dimethylaniline produced a diacetate. High-field 1H and 13C NMR techniques were used in the structure elucidation and assignment of the different NMR resonances of these three acetylated compounds.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Structure elucidation of 11‐amino‐8‐hydroxypentacyclo[5.4.0.0^{2, 6}.0^{3, 10}.0^{5, 9}]undecane‐8,11‐lactam through selective acetylation and complete ¹H and ¹³C NMR spectral assignment of the mono‐, di‐ and triacetates

Martins

Viljoen

Kruger

et al. 2004

Magnetic Reson in Chemistry

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“…The PCU dione 6 was converted to the 3,5-diallyl-4-oxahexacyclo[5.4.1.0 2,6 .0 3,10 .0 5,9 .0 8,11 ]dodecane 7 as described previously. [15,16] This diene 7 is an intermediate in the synthesis of all the derivatives 1-5 being investigated.…”

Section: Introductionmentioning

confidence: 99%

NMR elucidation of a novel (S)‐pentacyclo‐undecane bis‐(4‐phenyloxazoline) ligand and related derivatives

Boyle

Govender

Kruger

et al. 2008

Magnetic Reson in Chemistry

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The NMR elucidation of a novel ligand (S)-pentacyclo-undecane bis-(4-phenyloxazoline) and related pentacyclo-undecane (PCU) derivatives is reported. Two-dimensional NMR proved to be a powerful technique in overcoming the difficulties associated with the elucidation of these compounds when only one-dimensional NMR data is utilized. A chiral substituent was introduced to both 'arms' of the PCU skeleton to produce derivatives 1-3. These derivatives display C(1) symmetry with all thecage atoms being nonequivalent. Owing to overlapping of peaks in the (1)H spectra, identification of these diastereomeric protons was very difficult. The (13)C spectra gave rise to clear splitting of the nonequivalent carbons. This is unusual compared to similar PCU derivatives with chiral substituents as splitting of all the diastereomeric cage carbons has not yet been reported. Nuclear Overhauser enhancement spectroscopy (NOESY) correlations of derivatives 1-3 confirm the different conformations of the molecule in which the side 'arms' occupy different orientations with respect to cage moiety.

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“…Our own interest has focused on the reduction of ketonic carbonyl by hydride addition and we have considered the possibility that the hydride+carbonyl reaction might be susceptible also to analysis by structural correlation (Craze & Watt, 1981). To this end, a number of polycyclic hydroxyketones, exemplified by (1) to (4), have been prepared.…”

mentioning

confidence: 99%

A neutron diffraction study at 30 K of a cage compound, 5-hydroxy-7,10-dimethyltetracyclo[4.4.0.03,9.04,8]decan-2-one

Fenn¹,

Lehmann²,

Mills³

et al. 1989

Acta Crystallogr C

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Abstract. C12H~602, Mr= 192.3, monoclinic, P2Jc, a=10.744(3), b=15.211(4), c= 11.986 (3) A, fl = 93.94 (3) °, it = 1.2602 (2) A (from measurements on a ruby crystal), V=1954(1)A 3, Z=8, Dx= 1.31gcm -3, m.p. 357.2-357.7K, T=30K, R= 4.79% for 3196 reflexions. The structural unit is a dimer held together by weak hydrogen bonds. Dimerization occurs in two ways. Structural details for a reaction pathway involving intramolecular hydrogen 0108-2701/89/030423-06503.00 transfer of a methine hydrogen to a trans-annular keto-carbon atom are considered.

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Barriers to intramolecular hydride transfers in some polycyclic hydroxyketones

Cited by 40 publications

References 3 publications

Structure elucidation of 11‐amino‐8‐hydroxypentacyclo[5.4.0.0^{2, 6}.0^{3, 10}.0^{5, 9}]undecane‐8,11‐lactam through selective acetylation and complete ¹H and ¹³C NMR spectral assignment of the mono‐, di‐ and triacetates

Structure elucidation of 11‐amino‐8‐hydroxypentacyclo[5.4.0.0^{2, 6}.0^{3, 10}.0^{5, 9}]undecane‐8,11‐lactam through selective acetylation and complete ¹H and ¹³C NMR spectral assignment of the mono‐, di‐ and triacetates

NMR elucidation of a novel (S)‐pentacyclo‐undecane bis‐(4‐phenyloxazoline) ligand and related derivatives

A neutron diffraction study at 30 K of a cage compound, 5-hydroxy-7,10-dimethyltetracyclo[4.4.0.03,9.04,8]decan-2-one

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Barriers to intramolecular hydride transfers in some polycyclic hydroxyketones

Cited by 40 publications

References 3 publications

Structure elucidation of 11‐amino‐8‐hydroxypentacyclo[5.4.0.02, 6.03, 10.05, 9]undecane‐8,11‐lactam through selective acetylation and complete 1H and 13C NMR spectral assignment of the mono‐, di‐ and triacetates

Structure elucidation of 11‐amino‐8‐hydroxypentacyclo[5.4.0.02, 6.03, 10.05, 9]undecane‐8,11‐lactam through selective acetylation and complete 1H and 13C NMR spectral assignment of the mono‐, di‐ and triacetates

NMR elucidation of a novel (S)‐pentacyclo‐undecane bis‐(4‐phenyloxazoline) ligand and related derivatives

A neutron diffraction study at 30 K of a cage compound, 5-hydroxy-7,10-dimethyltetracyclo[4.4.0.03,9.04,8]decan-2-one

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Structure elucidation of 11‐amino‐8‐hydroxypentacyclo[5.4.0.0^{2, 6}.0^{3, 10}.0^{5, 9}]undecane‐8,11‐lactam through selective acetylation and complete ¹H and ¹³C NMR spectral assignment of the mono‐, di‐ and triacetates

Structure elucidation of 11‐amino‐8‐hydroxypentacyclo[5.4.0.0^{2, 6}.0^{3, 10}.0^{5, 9}]undecane‐8,11‐lactam through selective acetylation and complete ¹H and ¹³C NMR spectral assignment of the mono‐, di‐ and triacetates