On the total synthesis and determination of the absolute configuration of rishirilide B: Exploitation of subtle effects to control the sense of cycloaddition of o-quinodimethides

Kana Yamamoto, Martin F. Hentemann, John G. Allen, Samuel J. Danishefsky

研究成果: Article

27 引用 (Scopus)

抄録

The total synthesis of racemic rishirilide B has been accomplished. The synthesis serves to define the relative relationships of its stereogenic centers. Also, starting with readily available chiral pool, ent-rishirilide B was synthesized, thereby demonstrating that natural configuration of rishirilide B. The defining step in our total synthesis is the facile cycloreversion of the bis(siloxy)-benzocyclobutane and the intermolecular o-quinodimethide Diels-Alder cycloaddition. We believe that the tight regiochemical guidance in this step arises from a meshing of the electron-donating effects of the symmetry-perturbing aromatic OTBS group of the o-quinodimethide diene with the reactivity differential of the dienophile (enedione), modulated by the hydroxyl group at the α-position. The validity of the hypothesis of hydroxy-directed activation of its vicinal ketone function in the context of the enedione dienophile warrants further study. This type of activation may find broader applications in distinguishing reactivity profiles of key closely related functional groups in organic substrates.

元の言語English
ページ(範囲)3242-3252
ページ数11
ジャーナルChemistry - A European Journal
9
発行部数14
DOI
出版物ステータスPublished - 2003 7 21
外部発表Yes

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Cycloaddition
Chemical activation
Ketones
Hydroxyl Radical
Functional groups
Electrons
Substrates
rishirilide B

ASJC Scopus subject areas

  • Chemistry(all)

これを引用

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abstract = "The total synthesis of racemic rishirilide B has been accomplished. The synthesis serves to define the relative relationships of its stereogenic centers. Also, starting with readily available chiral pool, ent-rishirilide B was synthesized, thereby demonstrating that natural configuration of rishirilide B. The defining step in our total synthesis is the facile cycloreversion of the bis(siloxy)-benzocyclobutane and the intermolecular o-quinodimethide Diels-Alder cycloaddition. We believe that the tight regiochemical guidance in this step arises from a meshing of the electron-donating effects of the symmetry-perturbing aromatic OTBS group of the o-quinodimethide diene with the reactivity differential of the dienophile (enedione), modulated by the hydroxyl group at the α-position. The validity of the hypothesis of hydroxy-directed activation of its vicinal ketone function in the context of the enedione dienophile warrants further study. This type of activation may find broader applications in distinguishing reactivity profiles of key closely related functional groups in organic substrates.",
keywords = "Cycloaddition, Fused-ring systems, Quinodimethanes, Rishirilide, Total synthesis",
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T1 - On the total synthesis and determination of the absolute configuration of rishirilide B

T2 - Exploitation of subtle effects to control the sense of cycloaddition of o-quinodimethides

AU - Yamamoto, Kana

AU - Hentemann, Martin F.

AU - Allen, John G.

AU - Danishefsky, Samuel J.

PY - 2003/7/21

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N2 - The total synthesis of racemic rishirilide B has been accomplished. The synthesis serves to define the relative relationships of its stereogenic centers. Also, starting with readily available chiral pool, ent-rishirilide B was synthesized, thereby demonstrating that natural configuration of rishirilide B. The defining step in our total synthesis is the facile cycloreversion of the bis(siloxy)-benzocyclobutane and the intermolecular o-quinodimethide Diels-Alder cycloaddition. We believe that the tight regiochemical guidance in this step arises from a meshing of the electron-donating effects of the symmetry-perturbing aromatic OTBS group of the o-quinodimethide diene with the reactivity differential of the dienophile (enedione), modulated by the hydroxyl group at the α-position. The validity of the hypothesis of hydroxy-directed activation of its vicinal ketone function in the context of the enedione dienophile warrants further study. This type of activation may find broader applications in distinguishing reactivity profiles of key closely related functional groups in organic substrates.

AB - The total synthesis of racemic rishirilide B has been accomplished. The synthesis serves to define the relative relationships of its stereogenic centers. Also, starting with readily available chiral pool, ent-rishirilide B was synthesized, thereby demonstrating that natural configuration of rishirilide B. The defining step in our total synthesis is the facile cycloreversion of the bis(siloxy)-benzocyclobutane and the intermolecular o-quinodimethide Diels-Alder cycloaddition. We believe that the tight regiochemical guidance in this step arises from a meshing of the electron-donating effects of the symmetry-perturbing aromatic OTBS group of the o-quinodimethide diene with the reactivity differential of the dienophile (enedione), modulated by the hydroxyl group at the α-position. The validity of the hypothesis of hydroxy-directed activation of its vicinal ketone function in the context of the enedione dienophile warrants further study. This type of activation may find broader applications in distinguishing reactivity profiles of key closely related functional groups in organic substrates.

KW - Cycloaddition

KW - Fused-ring systems

KW - Quinodimethanes

KW - Rishirilide

KW - Total synthesis

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