Neighboring Carbon and Hydrogen. XI. Solvolysis of exo-Norbornyl p-Bromobenzenesulfonate<sup>1,2,3</sup>

Winstein, S.; Trifan, Daniel S.

doi:10.1021/ja01125a007

Cited by 132 publications

(40 citation statements)

References 1 publication

(4 reference statements)

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“…To a t-butyl methyl ether (50 mL) solution of racemic (±)-endo-2-norborneol (44.6 mmol) and vinyl acetate (10 mL), porcine pancreatic lipase (30 g [34][35][36][37][38] ) was obtained from basic hydrolysis (0.1 M KOH) of (R)-endo-norbornyl butyrate in ethanol (95%) in 99% yield. The enantiomeric excess (e.e.)…”

Section: (S)-(-)-endo-and (R)-(+)-endo-2-norborneol (Scheme 2)mentioning

confidence: 99%

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Stereoselective inhibition of butyrylcholinesterase by enantiomers ofexo- andendo-2-norbornyl-N-n-butylcarbamates

Chiou

Huang

Yeh

et al. 2009

Journal of Enzyme Inhibition and Medicinal Chemistry

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Section: (S)-(-)-endo-and (R)-(+)-endo-2-norborneol (Scheme 2)mentioning

confidence: 99%

“…Duplicate sets of data were collected for each inhibitor concentration. [34][35][36][37][38] and the 19 F-NMR spectra of their Mosher's ester derivatives [39][40][41] (Table 1 and Scheme 3).…”

mentioning

confidence: 99%

Stereoselective inhibition of butyrylcholinesterase by enantiomers ofexo- andendo-2-norbornyl-N-n-butylcarbamates

Chiou

Huang

Yeh

et al. 2009

Journal of Enzyme Inhibition and Medicinal Chemistry

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“…Existing information (4,5) on the solvolyses of exo-norbornpl derivatives indicates the operation of unimolecular reactions possibly complicated, however, by internal return froill a reactive ion-pair intermediate. I-Ience, the appropi-iate form of the Broilsted rate law for the system under study is equation [l] (1,6) where k is the observed first-order specific rate constant for the productioll of acid, 1 1 is the I-Ienry's law constant for distribution of exo-norbornyl bromide between the solution ancl the gas phase, F is a factor of constitution clependent upon the precise course of reaction ( I ) , the prilned symbols refer to a salt solution, and the unprilned symbols to the reference solution, the pure solvent.…”

Section: Salt Effects I N the Solvolysis Of Exo-norbornyi Bromidel'mentioning

confidence: 99%

SOLVATION EFFECTS AND RELATIVE RATES III. SALT EFFECTS IN THE SOLVOLYSIS OF exo-NORBORNYL BROMIDE

McMichael¹,

Clément²

1961

Can. J. Chem.

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It is remarkable that all of the 1: 1 compouncls crystallize in the distorted NiAs (MnP) structure rather than the NiAs structure itself. In the palladium and platinum systems where one might anticipate the NiAs structure no 1: 1 compounds were obtained.The diphosphides, diarsenicles, and diantimonides of ruthenium and osinium have the marcasite structure, while the corresponding compouncls of palladium and platinum have the pyrite structure. The rather complicated diffraction patterns of RhAs, and IrAs? are most certainly related, ancl bear a distinct similarity to the pattern of CoAs, (8). A strong low-order reflection in the CoAs2 pattern is split in the RhAs, and IrAs2 patterns; this leacls us to doubt the orthoi-hombic cell we proposed earlier for CoAs2. These diarsenides may prove to be isostruct~iral with the rhodi~im ancl iriclium diphosphides mentioned by Rundqvist.Since the tripl~ospl~icles and triantimonicles of cobalt, rhodium, and iridium are known to have the cubic CoAs:, structure, it is not surprising that RhAs:! and 1 1 -A~~ have the same structure. The list of compouncls crystallizing in the sltutterudite systenl now stands a t 1 I , ancl insofar as binary pnicticles are concerned, call be considered to be complete. With the exception of NIP, ancl PclI's they are formed only by the cobalt family of transition metals. Bism~itl~ides with this structure have not been observed.'I'hese systems arc no\v being st~icliecl in some detail.

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“…[5][6][7][8] Different experimental approaches indicated the influence of anchimeric assistance on the solvolysis of 2-exonorbornyl tosylate. [9][10][11][12][13][14] In addition, it was established the nucleophilically unassisted character of 2-exo-norbornyl tosylate solvolysis.…”

Section: Introductionmentioning

confidence: 99%

Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol

Firme¹

2012

J. Braz. Chem. Soc.

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A assistência da deslocalização de elétrons sigma ou assistência anquimérica dos elétrons sigma explica grandes diferenças de velocidade na solvólise de 2-exo-e 2-endo-norbornilp-bromobenzenosulfonatos. Este estudo foi anteriormente analisado pela teoria dos orbitais moleculares em fase gás. Ao revisitar este antigo problema a partir da teoria quântica de átomos em moléculas (QTAIM), novas informações sobre essas reações foram obtidas. Os resultados de QTAIM mostram que, na primeira etapa da solvólise não assistida nucleofilicamente dos alcoóis protonados 2-exo-norbornanol e 2-endo-norbornanol, ambas as reações são anquimericamente assistidas pela participação de elétrons sigma. Similarmente, na primeira etapa da solvólise não assistida nucleofilicamente dos álcoois protonados 2-endo-oxabicicloheptanol e 2-exooxabicicloheptanol, os resultados de QTAIM mostram que ambas as reações são anquimericamente assistidas: a primeira a partir da participação da ligação sigma C-O e de pares de elétrons isolados do oxigênio e a última a partir da participação da ligação sigma C1-C2. The assistance of s electron delocalization or anchimeric assistance of s electrons accounts for the large rate differences in the solvolysis of 2-exo-and 2-endo-norbornylp-bromobenzenesulfonates. This study was formerly analyzed by molecular orbital theory in gas phase. By revisiting this old problem from the quantum theory of atoms in molecules (QTAIM), new information on these reactions was obtained. The QTAIM results show that, in the first step of the nucleophilically unassisted solvolysis of protonated 2-exo-norbornanol and of protonated 2-endo-norbornanol, both reactions are anchimerically assisted by sigma bond participation. Similarly, in the first step of the nucleophilically unassisted solvolysis of protonated 2-endooxabicycloheptanol and of protonated 2-exo-oxabicycloheptanol, the QTAIM results show that both reactions are anchimerically assisted: the former from sigma bond participation from O-C bonds and valence shell electron participation from oxygen atom and the latter from sigma bond participation from C1-C2 bond.

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Neighboring Carbon and Hydrogen. XI. Solvolysis of exo-Norbornyl p-Bromobenzenesulfonate^1,2,3

Cited by 132 publications

References 1 publication

Stereoselective inhibition of butyrylcholinesterase by enantiomers ofexo- andendo-2-norbornyl-N-n-butylcarbamates

Stereoselective inhibition of butyrylcholinesterase by enantiomers ofexo- andendo-2-norbornyl-N-n-butylcarbamates

SOLVATION EFFECTS AND RELATIVE RATES III. SALT EFFECTS IN THE SOLVOLYSIS OF exo-NORBORNYL BROMIDE

Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol

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Neighboring Carbon and Hydrogen. XI. Solvolysis of exo-Norbornyl p-Bromobenzenesulfonate1,2,3

Cited by 132 publications

References 1 publication

Stereoselective inhibition of butyrylcholinesterase by enantiomers ofexo- andendo-2-norbornyl-N-n-butylcarbamates

Stereoselective inhibition of butyrylcholinesterase by enantiomers ofexo- andendo-2-norbornyl-N-n-butylcarbamates

SOLVATION EFFECTS AND RELATIVE RATES III. SALT EFFECTS IN THE SOLVOLYSIS OF exo-NORBORNYL BROMIDE

Topological study of the first step of nucleophilically unassisted solvolysis of protonated 2-endo/exo-norbornanol and protonated 2-endo/exo-oxabicycloheptanol

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Neighboring Carbon and Hydrogen. XI. Solvolysis of exo-Norbornyl p-Bromobenzenesulfonate^1,2,3