Intramolecular Diels-Alder reactions: the angularly methylated trans-perhydroindan ring system

Roush, William; Peseckis, Steven M.

doi:10.1021/ja00412a027

Cited by 64 publications

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“…While certain types of stereochemical flexibility (for example, the ability to achieve both exo and endo relative face selectivity in a Diels–Alder reaction process) are sometimes difficult to achieve in intermolecular reactions, there are a number of examples of this type of stereochemical control in intramolecular transformations. In the Diels–Alder example, Alder's “ endo rule” is often not obeyed when the reaction is performed in the intramolecular mode 26. In this case, subtle changes in the structure of substrates can exert powerful effects on the stereochemical outcome of intramolecular reactions that produce new stereogenic centers 26–28.…”

Section: Diversity‐generating Processes and Their Use In Dos To Gementioning

confidence: 99%

“…In the Diels–Alder example, Alder's “ endo rule” is often not obeyed when the reaction is performed in the intramolecular mode 26. In this case, subtle changes in the structure of substrates can exert powerful effects on the stereochemical outcome of intramolecular reactions that produce new stereogenic centers 26–28. Such controlling elements may prove to be valuable for achieving stereochemical diversity in DOS.…”

Section: Diversity‐generating Processes and Their Use In Dos To Gementioning

confidence: 99%

“…For example, Roush and co‐workers found that the position of the activating carbonyl group of the dienophile in substrates such as 24 and 26 can control exo versus endo selectivity for intramolecular Diels–Alder reactions (Scheme ) 26. Substrate 24 , with an activating aldehyde group on the internal position of the dienophile, yields predominantly the cis ‐fused perhydroindan ring system ( exo product).…”

Section: Diversity‐generating Processes and Their Use In Dos To Gementioning

confidence: 99%

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A Planning Strategy for Diversity‐Oriented Synthesis

2003

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In contrast to target-oriented synthesis (TOS) and medicinal or combinatorial chemistry, which aim to access precise or dense regions of chemistry space, diversity-oriented synthesis (DOS) populates chemical space broadly with small-molecules having diverse structures. The goals of DOS include the development of pathways leading to the efficient (three- to five-step) synthesis of collections of small molecules having skeletal and stereochemical diversity with defined coordinates in chemical space. Ideally, these pathways also yield compounds having the potential to attach appendages site- and stereoselectively to a variety of attachment sites during a post-screening, maturation stage. The diverse skeletons and stereochemistries ensure that the appendages can be positioned in multiple orientations about the surface of the molecules. TOS as well as medicinal and combinatorial chemistries have been advanced by the development of retrosynthetic analysis. Although the distinct goals of DOS do not permit the application of retrosynthetic concepts and thinking, these foundations are being built on, by using parallel logic, to develop a complementary procedure known as forward-synthetic analysis. This analysis facilitates synthetic planning, communication, and teaching in this evolving discipline.

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Section: Diversity‐generating Processes and Their Use In Dos To Gementioning

confidence: 99%

Section: Diversity‐generating Processes and Their Use In Dos To Gementioning

confidence: 99%

Section: Diversity‐generating Processes and Their Use In Dos To Gementioning

confidence: 99%

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A Planning Strategy for Diversity‐Oriented Synthesis

2003

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“…B. die exo ‐ und endo ‐Seitenselektivität von Diels‐Alder‐Reaktionen) bei intermolekularen Reaktionen manchmal nur schwer zu beeinflussen ist, gibt es einige Beispiele für eine vergleichbare stereochemische Kontrolle bei intramolekularen Umwandlungen. Bei intramolekularen Diels‐Alder‐Reaktionen wird die “ endo ‐Regel” oft nicht befolgt 26. Hier können kleine Änderungen in der Substratstruktur die Konfiguration neu gebildeter stereogener Zentren der Produkte entscheidend beeinflussen 26–28…”

Section: Diversitäts‐erzeugende Prozesse In Dos‐strategien (äHnlicunclassified

“…Bei intramolekularen Diels‐Alder‐Reaktionen wird die “ endo ‐Regel” oft nicht befolgt 26. Hier können kleine Änderungen in der Substratstruktur die Konfiguration neu gebildeter stereogener Zentren der Produkte entscheidend beeinflussen 26–28…”

Section: Diversitäts‐erzeugende Prozesse In Dos‐strategien (äHnlicunclassified

Eine Strategie für die Diversitäts‐orientierte Synthese

Burke¹,

Schreiber²

2003

Angewandte Chemie

293

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Anders als die Target‐orientierte Synthese (TOS) und die medizinische oder kombinatorische Chemie, die den Zugang zu einem bestimmten, oft engen Bereich des chemischen Raums anstreben, füllt die Diversitäts‐orientierte Synthese (DOS) den chemischen Raum mit kleinen Molekülen unterschiedlichster Strukturen. Hauptziel von DOS ist es, einen effizienten, drei‐ bis fünfstufigen Zugang zu Kollektiven kleiner Moleküle mit hoher stereochemischer Diversität und Molekülgerüst‐Diversität zu schaffen, die definierte Koordinaten im chemischen Raum einnehmen. Idealerweise erhält man dabei Verbindungen, die nach dem Screening regio‐ und stereoselektiv funktionalisiert werden können. Stereochemische Diversität und Molekülgerüst‐Diversität stellen sicher, dass die Bausteine an der Moleküloberfläche in verschiedenen Ausrichtungen gebunden werden können. Die Retrosynthese war ein Fortschritt für TOS, für die medizinische und die kombinatorische Chemie. Obwohl die Ziele von DOS die Anwendung einer Retrosynthese nicht vorsehen, kann man eine komplementäre Vorgehensweise entwickeln: die vorwärtssynthetische Analyse (forward synthetic‐analysis). Dieses Konzept erleichtert die Entwicklung, die Beschreibung und das Unterrichten von DOS.

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3,3-Diethoxy-1-propen-2-ylcopper

Linderman

2001

Encyclopedia of Reagents for Organic Synthesis

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Intramolecular Diels-Alder reactions: the angularly methylated trans-perhydroindan ring system

Cited by 64 publications

References 0 publications

A Planning Strategy for Diversity‐Oriented Synthesis

A Planning Strategy for Diversity‐Oriented Synthesis

Eine Strategie für die Diversitäts‐orientierte Synthese

3,3-Diethoxy-1-propen-2-ylcopper

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