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Studies Toward the Enantioselective Synthesis of Briarane Diterpenes.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Studies Toward the Enantioselective Synthesis of Briarane Diterpenes./
Author:	Farr, Joshua Daniel.
Description:	1 online resource (200 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 84-04, Section: B.
Contained By:	Dissertations Abstracts International84-04B.
Subject:	Aluminum. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=29408088click for full text (PQDT)
ISBN:	9798352650349

Studies Toward the Enantioselective Synthesis of Briarane Diterpenes.
Farr, Joshua Daniel.

Studies Toward the Enantioselective Synthesis of Briarane Diterpenes. - 1 online resource (200 pages)

Source: Dissertations Abstracts International, Volume: 84-04, Section: B.

Thesis (Ph.D.)--Stanford University, 2022.

Includes bibliographical references

First isolated over fifty years ago, the briaranes are a diverse family of approximately 800 diterpenoid natural products that are unified by a unique carbon skeleton which houses a trans-[8.4.0]-tetradecane ring system. This natural product family collectively possesses a broad range of interesting bioactivity and several unusual structural features, such as halogen-bearing stereocenters. This, in combination with the presence of multiple highly conserved structural features has attracted the attention of synthetic chemists for the last three decades. Despite considerable effort, no successful synthesis of any member of this family has been reported in the literature.At the outset of our work, the reports toward these natural products focused largely on the synthesis of structural motifs, rather than targeting the synthesis of any specific member. A synthesis which succeeded in establishing these important motifs in a streamlined manner as well as incorporating the rest of the carbon skeleton was completely unknown. Our group targeted a representative member, (+)-briareolide J, for synthesis, with the goal that the successful development of a route toward this member would enable the synthesis of other structurally related members which differ only by oxidation state.We developed a first-generation approach toward these natural products which hinged on the convergent coupling of two fragments using an enantioselective aldol reaction. Further elaboration of this coupled product enabled the installation of important structural motifs while incorporating necessary functionality to complete the synthesis. Ultimately, we found that our final disconnection was not able to establish the challenging trans-[8.4.0]-tetradecane ring system, leading us to revise our synthetic strategy.Targeting a redesigned second-generation synthesis, we developed a radical-polar crossover reaction to couple two enantioenriched fragments, establishing an array of important structural motifs in a single step. Further elaboration of this intermediate afforded an advanced precursor containing all the carbon atoms needed to complete the synthesis. However, we once again found that this intermediate was incapable of forming the trans-[8.4.0]-tetradecane ring system through our planned disconnection. Lastly, model studies helped to establish possible root causes of these challenges, prompting us to once again redesign our synthetic strategy. Although ultimately unsuccessful, the insights from these studies pave the way for future synthetic endeavors.

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2023

Mode of access: World Wide Web

ISBN: 9798352650349Subjects--Topical Terms:

735071
Aluminum.
Index Terms--Genre/Form:

542853
Electronic books.

Studies Toward the Enantioselective Synthesis of Briarane Diterpenes.
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100 1 $a Farr, Joshua Daniel. $3 3704230
245 1 0 $a Studies Toward the Enantioselective Synthesis of Briarane Diterpenes.
264 0 $c 2022
300 $a 1 online resource (200 pages)
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500 $a Source: Dissertations Abstracts International, Volume: 84-04, Section: B.
500 $a Advisor: Chen, James Kenneth ; du Bois, Justin ; Burns, Noah Z.
502 $a Thesis (Ph.D.)--Stanford University, 2022.
504 $a Includes bibliographical references
520 $a First isolated over fifty years ago, the briaranes are a diverse family of approximately 800 diterpenoid natural products that are unified by a unique carbon skeleton which houses a trans-[8.4.0]-tetradecane ring system. This natural product family collectively possesses a broad range of interesting bioactivity and several unusual structural features, such as halogen-bearing stereocenters. This, in combination with the presence of multiple highly conserved structural features has attracted the attention of synthetic chemists for the last three decades. Despite considerable effort, no successful synthesis of any member of this family has been reported in the literature.At the outset of our work, the reports toward these natural products focused largely on the synthesis of structural motifs, rather than targeting the synthesis of any specific member. A synthesis which succeeded in establishing these important motifs in a streamlined manner as well as incorporating the rest of the carbon skeleton was completely unknown. Our group targeted a representative member, (+)-briareolide J, for synthesis, with the goal that the successful development of a route toward this member would enable the synthesis of other structurally related members which differ only by oxidation state.We developed a first-generation approach toward these natural products which hinged on the convergent coupling of two fragments using an enantioselective aldol reaction. Further elaboration of this coupled product enabled the installation of important structural motifs while incorporating necessary functionality to complete the synthesis. Ultimately, we found that our final disconnection was not able to establish the challenging trans-[8.4.0]-tetradecane ring system, leading us to revise our synthetic strategy.Targeting a redesigned second-generation synthesis, we developed a radical-polar crossover reaction to couple two enantioenriched fragments, establishing an array of important structural motifs in a single step. Further elaboration of this intermediate afforded an advanced precursor containing all the carbon atoms needed to complete the synthesis. However, we once again found that this intermediate was incapable of forming the trans-[8.4.0]-tetradecane ring system through our planned disconnection. Lastly, model studies helped to establish possible root causes of these challenges, prompting us to once again redesign our synthetic strategy. Although ultimately unsuccessful, the insights from these studies pave the way for future synthetic endeavors.
533 $a Electronic reproduction. $b Ann Arbor, Mich. : $c ProQuest, $d 2023
538 $a Mode of access: World Wide Web
650 4 $a Aluminum. $3 735071
650 4 $a Alcohol. $3 872287
650 4 $a Chlorine. $3 3566265
650 4 $a Natural products. $3 604625
650 4 $a Biosynthesis. $3 516407
650 4 $a Carbon. $3 604057
650 4 $a Biological activity. $3 3699913
650 4 $a Optimization. $3 891104
650 4 $a Organic chemistry. $3 523952
655 7 $a Electronic books. $2 lcsh $3 542853
690 $a 0490
710 2 $a ProQuest Information and Learning Co. $3 783688
710 2 $a Stanford University. $3 754827
773 0 $t Dissertations Abstracts International $g 84-04B.
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=29408088 $z click for full text (PQDT)