Cyclopamine and Congeners

Heretsch, Philipp; Giannis, Athanassios

doi:10.1002/9783527676545.ch15

Methods and Principles in Medicinal Chemistry

2014

DOI: 10.1002/9783527676545.ch15

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Cyclopamine and Congeners

Philipp Heretsch

Athanassios Giannis

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Cited by 3 publications

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“…Despite being the largest subclass of the Veratrum familymore than 70 members in total have been isolated to dateonly one of them has yielded to chemical synthesis ( vide infra ). As opposed to their cevanine counterparts, the veratramine and jervine types are more investigated in terms of their synthesis and therapeutic potential. − These members can be characterized by either the absence of an E ring or its inclusion as a spirofuran motif (cf. namesake compounds veratramine ( 5 ) and jervine ( 6 ), respectively).…”

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confidence: 99%

Enantioselective Total Synthesis of (+)-Heilonine

Cassaidy

Rawal

2021

J. Am. Chem. Soc.

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Chemical transformations that rapidly and efficiently construct a high level of molecular complexity in a single step are perhaps the most valuable in total synthesis. Among such transformations is the transition metal catalyzed [2 + 2 + 2] cycloisomerization reaction, which forges three new C–C bonds and one or more rings in a single synthetic operation. We report here a strategy that leverages this transformation to open de novo access to the Veratrum family of alkaloids. The highly convergent approach described herein includes (i) the enantioselective synthesis of a diyne fragment containing the steroidal A/B rings, (ii) the asymmetric synthesis of a propargyl-substituted piperidinone (F ring) unit, (iii) the high-yielding union of the above fragments, and (iv) the intramolecular [2 + 2 + 2] cycloisomerization reaction of the resulting carbon framework to construct in a single step the remaining three rings (C/D/E) of the hexacyclic cevanine skeleton. Efficient late-stage maneuvers culminated in the first total synthesis of heilonine (1), achieved in 21 steps starting from ethyl vinyl ketone.

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Enantioselective Total Synthesis of (+)-Heilonine

Cassaidy

Rawal

2021

J. Am. Chem. Soc.

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Asymmetric Synthesis of Cyclopamine, a Hedgehog (Hh) Signaling Pathway Inhibitor

Shao,

Liu,

Liu

et al. 2023

J. Am. Chem. Soc.

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Cyclopamine is a teratogenic steroidal alkaloid, which inhibits the Hedgehog (Hh) signaling pathway by targeting the Smoothened (Smo) receptor. Suppression of Hh signaling with synthetic small molecules has been pursued as a therapeutic approach for the treatment of cancer. We report herein the asymmetric synthesis of cyclopamine based on a two-stage relay strategy. Stage-I: total synthesis of veratramine through a convergent approach, wherein a crucial photoinduced excited-state Nazarov reaction was applied to construct the basic [6–6–5–6] skeleton of C-nor-D-homo-steroid. Stage-II: conversion of veratramine to cyclopamine was achieved through a sequence of chemo-selective redox manipulations.

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Ring Rearrangement Metathesis in 7-Oxabicyclo[2.2.1]heptene (7-Oxanorbornene) Derivatives. Some Applications in Natural Product Chemistry

Roscales

Plumet

2017

Natural Product Communications

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Metathesis reactions is firmly established as a valuable synthetic tool in organic chemistry, clearly comparable with the venerable Diels-Alder and Wittig reactions and, more recently, with the metal-catalyzed cross-coupling reactions. Metathesis reactions can be considered as a fascinating synthetic methodology, allowing different variants regarding substrate (alkene and alkyne metathesis) and type of metathetical reactions. On the other hand, tandem metathesis reactions such Ring Rearrangement Metathesis (RRM) and the coupling of metathesis reaction with other reactions of alkenes such as Diels-Alder or Heck reactions, makes metathesis one of the most powerful and reliable synthetic procedure. In particular, Ring-Rearrangement Metathesis (RRM) refers to the combination of several metathesis transformations into a domino process such as ringopening metathesis (ROM)/ring-closing metathesis (RCM) and ROM-cross metathesis (CM) in a one-pot operation. RRM delivers complex frameworks that are difficult to assemble by conventional methods constitutingan atom economic process. RRM is applicable to mono-and polycyclic systems of varying ring sizes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, pyran systems, bicyclo[2.2.1]heptene derivatives, bicyclo[2.2.2]octene derivatives, bicyclo[3.2.1]octene derivatives and bicyclo[3.2.1]octene derivatives. In this review our attention has focused on the RRM reactions in 7-oxabicyclo[2.2.1]heptene derivatives and on their application in the synthesis of natural products or significant subunits of them.

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Cyclopamine and Congeners

Cited by 3 publications

References 86 publications

Enantioselective Total Synthesis of (+)-Heilonine

Enantioselective Total Synthesis of (+)-Heilonine

Asymmetric Synthesis of Cyclopamine, a Hedgehog (Hh) Signaling Pathway Inhibitor

Ring Rearrangement Metathesis in 7-Oxabicyclo[2.2.1]heptene (7-Oxanorbornene) Derivatives. Some Applications in Natural Product Chemistry

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