Rapid intramolecular 1,4-hydride transfer across a rigid 4-hydroxycycloheptanone

Robert Cernik; Gabrielle Anne Craze; Owen S Mills; Ian Watt

Rapid intramolecular 1,4-hydride transfer across a rigid 4-hydroxycycloheptanone

Robert Cernik, Gabrielle Anne Craze, Owen S Mills, Ian Watt

Research output: Contribution to journal › Article › peer-review

Abstract

The 13C NMR of hydroxy ketone I (R = Na) was temp. dependent, behavior assocd. with rapid degenerate rearrangement involving intramol. hydride transfer from alkoxide to CO. Dynamic 13C NMR measurements gave a barrier to rearrangement of 13.7 kcal/mol at 4°. A much slower competing process giving hemiacetal II was obsd., and the mechanism of its formation is discussed. The mol. structure of I (R = p-O2NC6H4), detd. by x-ray crystallog., shows some pyramidalization for the ketonic CO group. [on SciFinder(R)]

Original language	English
Pages (from-to)	361-7
Number of pages	353
Journal	J. Chem. Soc., Perkin Trans. 2
Issue number	3
Publication status	Published - 1982

Keywords

Nuclear magnetic resonance (of carbon-13, in hydroxypentacyclododecanone and its derivs.)
Rearrangement (of hydroxypentacyclododecanone, hemiacetal by intramol.)
Crystal structure
Molecular structure (of pentacyclododecanonyl nitrobenzoate)
furanylpentacyclododecane
hemiacetal hydroxypentacyclododecanone intramol
rearrangement hydroxypentacyclododecanone
hydroxycycloheptanone intramol hydride transfer
cycloheptane hydroxy intramol hydride transfer
pentacyclododecanonyl nitrobenzoate crystal mol structure
NMR carbon 13 hydroxypentacyclododecanone

Cite this

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title = "Rapid intramolecular 1,4-hydride transfer across a rigid 4-hydroxycycloheptanone",

abstract = "The 13C NMR of hydroxy ketone I (R = Na) was temp. dependent, behavior assocd. with rapid degenerate rearrangement involving intramol. hydride transfer from alkoxide to CO. Dynamic 13C NMR measurements gave a barrier to rearrangement of 13.7 kcal/mol at 4°. A much slower competing process giving hemiacetal II was obsd., and the mechanism of its formation is discussed. The mol. structure of I (R = p-O2NC6H4), detd. by x-ray crystallog., shows some pyramidalization for the ketonic CO group. [on SciFinder(R)]",

keywords = "Nuclear magnetic resonance (of carbon-13, in hydroxypentacyclododecanone and its derivs.), Rearrangement (of hydroxypentacyclododecanone, hemiacetal by intramol.), Crystal structure, Molecular structure (of pentacyclododecanonyl nitrobenzoate), furanylpentacyclododecane, hemiacetal hydroxypentacyclododecanone intramol, rearrangement hydroxypentacyclododecanone, hydroxycycloheptanone intramol hydride transfer, cycloheptane hydroxy intramol hydride transfer, pentacyclododecanonyl nitrobenzoate crystal mol structure, NMR carbon 13 hydroxypentacyclododecanone",

author = "Robert Cernik and Craze, {Gabrielle Anne} and Mills, {Owen S} and Ian Watt",

note = "CAN 97:71731 Physical Organic Chemistry 82580-30-1P; 82598-41-2P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (prepn. and NMR of); 82580-31-2P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (prepn. and crystal and mol. structure of); 82580-29-8P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of); 6225-73-6 Role: RCT (Reactant), RACT (Reactant or reagent) (rearrangement of, hemiacetal by intramol.)",

year = "1982",

language = "English",

pages = "361--7",

journal = "Royal Chemical Society. Journal. Perkin Transactions 2 ",

issn = "1470-1820",

publisher = "Chemical Society",

number = "3",

}

TY - JOUR

T1 - Rapid intramolecular 1,4-hydride transfer across a rigid 4-hydroxycycloheptanone

AU - Cernik, Robert

AU - Craze, Gabrielle Anne

AU - Mills, Owen S

AU - Watt, Ian

N1 - CAN 97:71731 Physical Organic Chemistry 82580-30-1P; 82598-41-2P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (prepn. and NMR of); 82580-31-2P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (prepn. and crystal and mol. structure of); 82580-29-8P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of); 6225-73-6 Role: RCT (Reactant), RACT (Reactant or reagent) (rearrangement of, hemiacetal by intramol.)

PY - 1982

Y1 - 1982

N2 - The 13C NMR of hydroxy ketone I (R = Na) was temp. dependent, behavior assocd. with rapid degenerate rearrangement involving intramol. hydride transfer from alkoxide to CO. Dynamic 13C NMR measurements gave a barrier to rearrangement of 13.7 kcal/mol at 4°. A much slower competing process giving hemiacetal II was obsd., and the mechanism of its formation is discussed. The mol. structure of I (R = p-O2NC6H4), detd. by x-ray crystallog., shows some pyramidalization for the ketonic CO group. [on SciFinder(R)]

AB - The 13C NMR of hydroxy ketone I (R = Na) was temp. dependent, behavior assocd. with rapid degenerate rearrangement involving intramol. hydride transfer from alkoxide to CO. Dynamic 13C NMR measurements gave a barrier to rearrangement of 13.7 kcal/mol at 4°. A much slower competing process giving hemiacetal II was obsd., and the mechanism of its formation is discussed. The mol. structure of I (R = p-O2NC6H4), detd. by x-ray crystallog., shows some pyramidalization for the ketonic CO group. [on SciFinder(R)]

KW - Nuclear magnetic resonance (of carbon-13, in hydroxypentacyclododecanone and its derivs.)

KW - Rearrangement (of hydroxypentacyclododecanone, hemiacetal by intramol.)

KW - Crystal structure

KW - Molecular structure (of pentacyclododecanonyl nitrobenzoate)

KW - furanylpentacyclododecane

KW - hemiacetal hydroxypentacyclododecanone intramol

KW - rearrangement hydroxypentacyclododecanone

KW - hydroxycycloheptanone intramol hydride transfer

KW - cycloheptane hydroxy intramol hydride transfer

KW - pentacyclododecanonyl nitrobenzoate crystal mol structure

KW - NMR carbon 13 hydroxypentacyclododecanone

M3 - Article

SP - 361

EP - 367

JO - Royal Chemical Society. Journal. Perkin Transactions 2

JF - Royal Chemical Society. Journal. Perkin Transactions 2

SN - 1470-1820

IS - 3

ER -

Rapid intramolecular 1,4-hydride transfer across a rigid 4-hydroxycycloheptanone

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Keywords

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