Diastereotopic group selectivity and chemoselectivity of alkylidene carbene reactions on 8-oxabicyclo[3.2.1]oct-6-ene ring systems

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Diastereotopic group selectivity and chemoselectivity of alkylidene carbene reactions on 8-oxabicyclo[3.2.1]oct-6-ene ring systems. / Munro, Kevin R.; Male, Louise; Spencer, Neil; Grainger, Richard S.

In: Organic and Biomolecular Chemistry, Vol. 11, No. 39, 21.10.2013, p. 6856-6862.

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@article{cc52324125ce4243b4eb6ac8566772fe,
title = "Diastereotopic group selectivity and chemoselectivity of alkylidene carbene reactions on 8-oxabicyclo[3.2.1]oct-6-ene ring systems",
abstract = "α-Hydroxyalkylidene carbenes, generated from thermolysis of α,β-epoxy-N-aziridinylimines, undergo diastereotopic group selective 1,5 C–H insertion reactions on 2,4-dimethyl-8-oxabicyclo[3.2.1]oct-6-ene ring systems. Protection of a tertiary alcohol at C-3 of the bridged oxabicycle as a trimethylsilyl ether reverses the sense of diastereoselectivity. 1,5 C–H insertion into a methine adjacent to an OBn group, 1,5 O–R insertion into a tertiary alcohol (R = H) or silylether (R = TMS) at C-3 to form spirocyclic dihydrofurans, 1,2-rearrangement to an alkyne and fragmentation to a ketone are competing major pathways for 2-benzyloxy-substituted 8-oxabicyclo[3.2.1]oct-6-ene systems. Dihydrofuran formation is shown to be a result of substitution on the oxabicyclic ring system through comparison with other methods of alkylidene carbene formation.",
author = "Munro, {Kevin R.} and Louise Male and Neil Spencer and Grainger, {Richard S.}",
year = "2013",
month = oct,
day = "21",
doi = "10.1039/c3ob41390j",
language = "English",
volume = "11",
pages = "6856--6862",
journal = "Organic and Biomolecular Chemistry",
issn = "1477-0520",
publisher = "Royal Society of Chemistry",
number = "39",

}

RIS

TY - JOUR

T1 - Diastereotopic group selectivity and chemoselectivity of alkylidene carbene reactions on 8-oxabicyclo[3.2.1]oct-6-ene ring systems

AU - Munro, Kevin R.

AU - Male, Louise

AU - Spencer, Neil

AU - Grainger, Richard S.

PY - 2013/10/21

Y1 - 2013/10/21

N2 - α-Hydroxyalkylidene carbenes, generated from thermolysis of α,β-epoxy-N-aziridinylimines, undergo diastereotopic group selective 1,5 C–H insertion reactions on 2,4-dimethyl-8-oxabicyclo[3.2.1]oct-6-ene ring systems. Protection of a tertiary alcohol at C-3 of the bridged oxabicycle as a trimethylsilyl ether reverses the sense of diastereoselectivity. 1,5 C–H insertion into a methine adjacent to an OBn group, 1,5 O–R insertion into a tertiary alcohol (R = H) or silylether (R = TMS) at C-3 to form spirocyclic dihydrofurans, 1,2-rearrangement to an alkyne and fragmentation to a ketone are competing major pathways for 2-benzyloxy-substituted 8-oxabicyclo[3.2.1]oct-6-ene systems. Dihydrofuran formation is shown to be a result of substitution on the oxabicyclic ring system through comparison with other methods of alkylidene carbene formation.

AB - α-Hydroxyalkylidene carbenes, generated from thermolysis of α,β-epoxy-N-aziridinylimines, undergo diastereotopic group selective 1,5 C–H insertion reactions on 2,4-dimethyl-8-oxabicyclo[3.2.1]oct-6-ene ring systems. Protection of a tertiary alcohol at C-3 of the bridged oxabicycle as a trimethylsilyl ether reverses the sense of diastereoselectivity. 1,5 C–H insertion into a methine adjacent to an OBn group, 1,5 O–R insertion into a tertiary alcohol (R = H) or silylether (R = TMS) at C-3 to form spirocyclic dihydrofurans, 1,2-rearrangement to an alkyne and fragmentation to a ketone are competing major pathways for 2-benzyloxy-substituted 8-oxabicyclo[3.2.1]oct-6-ene systems. Dihydrofuran formation is shown to be a result of substitution on the oxabicyclic ring system through comparison with other methods of alkylidene carbene formation.

U2 - 10.1039/c3ob41390j

DO - 10.1039/c3ob41390j

M3 - Article

C2 - 24175334

VL - 11

SP - 6856

EP - 6862

JO - Organic and Biomolecular Chemistry

JF - Organic and Biomolecular Chemistry

SN - 1477-0520

IS - 39

ER -