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Development of Asymmetric Alkylation...

Jackson, Jeffrey James.

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Development of Asymmetric Alkylation Chemistry Using Chiral Lithium Amides and Application to the Total Synthesis of (+)-Dragmacidin D.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Development of Asymmetric Alkylation Chemistry Using Chiral Lithium Amides and Application to the Total Synthesis of (+)-Dragmacidin D./
作者:	Jackson, Jeffrey James.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, : 2016,
面頁冊數:	289 p.
附註:	Source: Dissertation Abstracts International, Volume: 78-02(E), Section: B.
Contained By:	Dissertation Abstracts International78-02B(E).
標題:	Organic chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=10159691
ISBN:	9781369146196

Development of Asymmetric Alkylation Chemistry Using Chiral Lithium Amides and Application to the Total Synthesis of (+)-Dragmacidin D.
Jackson, Jeffrey James.

Development of Asymmetric Alkylation Chemistry Using Chiral Lithium Amides and Application to the Total Synthesis of (+)-Dragmacidin D. - Ann Arbor : ProQuest Dissertations & Theses, 2016 - 289 p.

Source: Dissertation Abstracts International, Volume: 78-02(E), Section: B.

Thesis (Ph.D.)--University of California, Santa Barbara, 2016.

Asymmetric alkylation of enolates has been the subject of vigorous investigation for several decades as researchers are constantly aiming to increase the efficiency of stereoselective C--C bond constructions, a cornerstone in asymmetric synthesis. Furthermore, Michael addition is a premier synthetic method for carbon--carbon and carbon--heteroatom bond formation. Our group has recently developed a procedure utilizing the chiral reactive enediolate--dilithium amide aggregate of aryl- and hetereo-aryl acetic acids in enantioselective Michael additions to alpha,beta-unsaturated esters for asymmetric carbon-carbon bond formation, mediated by a dimeric chiral tetramine. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B. In addition, our preliminary studies also reveal the potential expansion of alkylation scope towards the synthesis of quaternary stereocenters.

ISBN: 9781369146196Subjects--Topical Terms:

523952
Organic chemistry.

Development of Asymmetric Alkylation Chemistry Using Chiral Lithium Amides and Application to the Total Synthesis of (+)-Dragmacidin D.
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245 1 0 $a Development of Asymmetric Alkylation Chemistry Using Chiral Lithium Amides and Application to the Total Synthesis of (+)-Dragmacidin D.
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500 $a Source: Dissertation Abstracts International, Volume: 78-02(E), Section: B.
500 $a Adviser: Armen Zakarian.
502 $a Thesis (Ph.D.)--University of California, Santa Barbara, 2016.
520 $a Asymmetric alkylation of enolates has been the subject of vigorous investigation for several decades as researchers are constantly aiming to increase the efficiency of stereoselective C--C bond constructions, a cornerstone in asymmetric synthesis. Furthermore, Michael addition is a premier synthetic method for carbon--carbon and carbon--heteroatom bond formation. Our group has recently developed a procedure utilizing the chiral reactive enediolate--dilithium amide aggregate of aryl- and hetereo-aryl acetic acids in enantioselective Michael additions to alpha,beta-unsaturated esters for asymmetric carbon-carbon bond formation, mediated by a dimeric chiral tetramine. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B. In addition, our preliminary studies also reveal the potential expansion of alkylation scope towards the synthesis of quaternary stereocenters.
520 $a Dragmacidin D is a member of a family of heterocyclic bis-indolyl alkaloids isolated from deep-water Caribbean sponges of Dragmacidon and Spongosorites sp. Although the initially isolated sample displayed no optical activity, subsequent reisolation provided a sample with an [alpha]D of +12° (c 0.95, EtOH). These observations indicate a certain measure of ambiguity for the stereochemical identity and configurational stability of its sole stereogenic center. The asymmetric synthesis of (+)-dragmacidin D was completed in 10 steps. Its sole stereocenter was set by a direct asymmetric alkylation enabled by a C2-symmetric tetramine and lithium N-(trimethylsilyl)-tert-butylamide as the key enolization reagent. A central Larock indole synthesis was employed in a convergent assembly of the heterocyclic subunits. The 2-aminoimidazole heterocycle was installed in a concise manner via a copper mediated acyl cross coupling reaction. The stereochemical evidence from this work strongly supports the predicted S configuration at the 6''' position, which is consistent with other members of the dragmacidin family of natural products.
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