Hetero-Diels-Alder reaction in highly functionalized natural product synthesis

1986 ◽  
Vol 19 (8) ◽  
pp. 250-259 ◽  
Author(s):  
Richard R. Schmidt
Keyword(s):  
Natural Product ◽  
Alder Reaction ◽  
Diels Alder ◽  
Natural Product Synthesis ◽  
Diels Alder Reaction

Formal synthesis of kingianin A based upon a novel electrochemically-induced radical cation Diels–Alder reaction

2014 ◽  
Vol 50 (83) ◽  
pp. 12523-12525 ◽  
Author(s):  
Jonathan C. Moore ◽  
E. Stephen Davies ◽  
Darren A. Walsh ◽  
Pallavi Sharma ◽  
John E. Moses
Keyword(s):  
Natural Product ◽  
Radical Cation ◽  
Alder Reaction ◽  
Diels Alder ◽  
Natural Product Synthesis ◽  
Electrochemical Reactions ◽  
Formal Synthesis ◽  
Diels Alder Reaction

The application of electrochemical reactions in natural product synthesis has burgeoned in recent years. We herein report a formal synthesis of the complex and dimeric natural product kingianin A, which employs an electrochemically-mediated radical cation Diels–Alder cycloaddition as the key step.

Masked Bisketenes as Diels–Alder Dienes

2020 ◽  
Author(s):  
Isuru Dissanayake ◽  
Jacob Hart ◽  
Emma Becroft ◽  
Christopher Sumby ◽  
Christopher Newton
Keyword(s):  
Natural Product ◽  
Ring Opening ◽  
Alder Reaction ◽  
Diels Alder ◽  
Natural Product Synthesis ◽  
One Pot ◽  
Neuroprotective Agent ◽  
Mild Conditions ◽  
Diels Alder Reaction

<div> <div> <div> <p>2,5-Bis(<i>tert</i>-butyldimethylsilyloxy)furans are established as masked vicinal bisketenes for application as dienes in the Diels–Alder reaction. Cycloaddition with olefinic dienophiles, under exceptionally mild conditions, enables convergent access to highly substituted <i>para</i>-hydroquinones in unprotected form via a one-pot Diels–Alder/ring-opening/tautomerization sequence. The synthesis of <i>para</i>-benzoquinones from acetylenic dienophiles, including benzynes, is also demonstrated, and 2,5-bis(<i>tert</i>-butyldimethylsilyloxy)pyrroles are established as competent dienes for the synthesis of <i>para</i>-iminoquinones. Application in natural product synthesis enables gram-scale access to the neuroprotective agent (±)-indanostatin. </p> </div> </div> </div>

Bisketene Equivalents as Diels–Alder Dienes

2020 ◽  
Author(s):  
Isuru Dissanayake ◽  
Jacob Hart ◽  
Emma Becroft ◽  
Christopher Sumby ◽  
Christopher Newton
Keyword(s):  
Natural Product ◽  
Ring Opening ◽  
Alder Reaction ◽  
Diels Alder ◽  
Natural Product Synthesis ◽  
One Pot ◽  
Neuroprotective Agent ◽  
Mild Conditions ◽  
Diels Alder Reaction

<div> <div> <div> <p>2,5-Bis(<i>tert</i>-butyldimethylsilyloxy)furans are established as vicinal bisketene equivalents for application as dienes in the Diels–Alder reaction. Cycloaddition with olefinic dienophiles, under exceptionally mild conditions, enables convergent access to highly substituted <i>para</i>-hydroquinones in unprotected form via a one-pot Diels–Alder/ring-opening/tautomerization sequence. The synthesis of <i>para</i>-benzoquinones from acetylenic dienophiles, including benzynes, is also demonstrated, and 2,5-bis(<i>tert</i>-butyldimethylsilyloxy)pyrroles are established as competent dienes for the synthesis of <i>para</i>-iminoquinones. Application in natural product synthesis enables gram-scale access to the neuroprotective agent (±)-indanostatin.</p> </div> </div> </div>

Development of methods suitable for natural product synthesis: The azadirachtin story

2005 ◽  
Vol 77 (7) ◽  
pp. 1115-1130 ◽  
Author(s):  
Steven V. Ley
Keyword(s):  
Natural Product ◽  
Claisen Rearrangement ◽  
Alder Reaction ◽  
Diels Alder ◽  
Natural Product Synthesis ◽  
Enol Ether ◽  
Ring Contraction ◽  
Left Hand ◽  
Diels Alder Reaction ◽  
Rearrangement Reaction

Our synthesis work on the insect antifeedant azadirachtin is described. Particular emphasis is placed on the key coupling of a left-hand decalin fragment with a right-hand hydroxydihydrofuran acetal unit via a Claisen rearrangement reaction of an intermediate propargylic enol ether. New chemistry has been developed leading to control of an endo-selective intramolecular Diels–Alder reaction using silicon, which was essential for the construction of the appropriately functionalized decalin fragment. In order to install the five-ring hemiacetal of azadirachtin, we also developed a new ring contraction protocol via an intermediate six-ring cyano ester.

Asymmetric Synthesis of 3,3′-Piperidinoyl Spirooxindoles and Discovery of Stereospecific Cycloadducts as Novel Hedgehog Pathway Modulators

Synthesis ◽  
2020 ◽  
Vol 52 (21) ◽  
pp. 3140-3152
Author(s):  
Kamal Kumar ◽  
Mohammad Rehan ◽  
Jana Flegel ◽  
Franziska Heitkamp ◽  
Jorgelina L. Pergomet ◽  
...  
Keyword(s):  
Transition Metal ◽  
Small Molecules ◽  
Asymmetric Synthesis ◽  
Natural Product ◽  
Transition Metal Complexes ◽  
Alder Reaction ◽  
Diels Alder ◽  
Hedgehog Pathway ◽  
Diels Alder Reaction ◽  
Efficient Access

An enantioselective hetero-Diels–Alder reaction of alkylidene­ oxindoles and 2-aza-3-silyloxy-1,3-butadienes, catalyzed by divalent transition metal complexes with N,N′-dioxide ligands offered an efficient access to natural-product-based 3,3′-piperidinoyl spiroox­indole class of small molecules. exo-Cycloadducts formed via stereospecific cycloaddition with Z-olefin displayed potent activity in modulation of hedgehog pathway.

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