Synthesis of a cis-5-cyclodecenone and cis fused hydronaphthalenols through control of the stereochemistry of the oxy-Cope rearrangement with the tri-n-propylsilyl substituent

Chu, Yongliang; Colclough, David; Hotchkin, D.; Tuazon, M.; White, James B.

doi:10.1016/s0040-4020(97)00952-6

Cited by 9 publications

(1 citation statement)

References 17 publications

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“…Similar differences in the rate and selectivity of the deprotection of isomers have been reported previously. [14] We inferred that the loss of 5 % ee in the final natural product 23 was brought about by isomerization of the double bond in (Z)-(S)-11g to give (E)-(S)-11g during the desilylation step. [15] However, both the preference for E configuration and the high degree of chirality transfer in going from (R)-8b to (R)-11g instructively confirm the mechanistic model deduced earlier.…”

Section: Resultsmentioning

confidence: 99%

Removable Silyl Group as a “Masked Proton” in Oxy‐2‐oxonia(azonia)‐Cope Rearrangement: Applications in Stereoselective Total Synthesis of Natural Macrolides

Zou

Zhou

et al. 2015

Eur J Org Chem

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In the presence of a Lewis acid, trimethylsilyl‐substituted β,γ‐unsaturated ketones and aldehydes (imines) undergo nucleophilic addition to produce zwitterionic intermediates, followed by oxy‐2‐oxonia(azonia)‐Cope rearrangements to give homoallylic esters (amides). In the case of TMS‐containing 2‐vinylcycloalkanones, the process results in ring‐enlargement, providing 10‐ to 16‐membered lactones. This protocol was applied to the total synthesis of (R)‐phoracantholide I.

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Section: Resultsmentioning

confidence: 99%

Removable Silyl Group as a “Masked Proton” in Oxy‐2‐oxonia(azonia)‐Cope Rearrangement: Applications in Stereoselective Total Synthesis of Natural Macrolides

Zou

Zhou

et al. 2015

Eur J Org Chem

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Planar Chirality − Synthesis and Transformations of 8- to 10-Membered Heterocycles Bearing (E)-Olefins

Nubbemeyer

2001

Eur. J. Org. Chem.

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Medium‐sized heterocycles (8‐membered to 10‐membered) are prevalently found in organic chemistry as key intermediates in the synthesis of more complex structures or as core structures in natural products or pharmaceutically important compounds. At present, the production of such rings remains a challenge in organic synthesis. During the past decade, an increasing amount of interest has focused on the generation of cyclic lactones and peptides, as well as on hairpins and β‐turn mimics, and such medium‐sized rings were thought to represent suitable fragments. Furthermore, heterocyclic structures of this type are a characteristic of a range of complex natural products, and total synthesis of these is a broad field for organic chemists to test new strategies and to develop new methods. The aim of this review is to discus some modern strategies for synthesizing unsaturated 8‐ to 10‐membered heterocycles, with the scope restricted to the production of ring systems incorporating a N, O, and S function in combination with (E)‐olefins. The planar‐chiral properties thus induced have been exploited for further stereoselective and regioselective reactions. Although a number of conversions has described only the generation of simple structures without complicated stereogenic properties, most of them seem to offer undiscovered potential in terms of stereoselective syntheses. However, the emphasis of the methods is focused on stereoselective processes. The review is subdivided into two major chapters: ring‐closure and ring‐enlargement reactions, and additional information is given on cycloadditions and fragmentations.

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ChemInform Abstract: Synthesis of a cis‐5‐Cyclodecenone and cis‐Fused Hydronaphthalenols Through Control of the Stereochemistry of the Oxy‐Cope Rearrangement with the Tri‐n‐propylsilyl Substituent.

et al. 1998

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Synthesis of a cis-5-cyclodecenone and cis fused hydronaphthalenols through control of the stereochemistry of the oxy-Cope rearrangement with the tri-n-propylsilyl substituent

Cited by 9 publications

References 17 publications

Removable Silyl Group as a “Masked Proton” in Oxy‐2‐oxonia(azonia)‐Cope Rearrangement: Applications in Stereoselective Total Synthesis of Natural Macrolides

Removable Silyl Group as a “Masked Proton” in Oxy‐2‐oxonia(azonia)‐Cope Rearrangement: Applications in Stereoselective Total Synthesis of Natural Macrolides

Planar Chirality − Synthesis and Transformations of 8- to 10-Membered Heterocycles Bearing (E)-Olefins

ChemInform Abstract: Synthesis of a cis‐5‐Cyclodecenone and cis‐Fused Hydronaphthalenols Through Control of the Stereochemistry of the Oxy‐Cope Rearrangement with the Tri‐n‐propylsilyl Substituent.

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