東華大學圖書館 |

Language: English

Help

回圖書館首頁

手機版館藏查詢

Back

Switch To: Labeled | MARC Mode | ISBD

New reactions of ketones with hydrox...

Gracias, Vijaya Judith,

Linked to FindBook

Google Book

Amazon

博客來

New reactions of ketones with hydroxy azides and the application of the intramolecular Schmidt reaction toward the total synthesis of lasubines I and II /

Record Type:	Electronic resources : Monograph/item
Title/Author:	New reactions of ketones with hydroxy azides and the application of the intramolecular Schmidt reaction toward the total synthesis of lasubines I and II // Vijaya Judith Gracias.
Author:	Gracias, Vijaya Judith,
Description:	1 electronic resource (183 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 60-06, Section: B.
Contained By:	Dissertations Abstracts International60-06B.
Subject:	Pharmacology. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9904804
ISBN:	9780599021181

New reactions of ketones with hydroxy azides and the application of the intramolecular Schmidt reaction toward the total synthesis of lasubines I and II /
Gracias, Vijaya Judith,

New reactions of ketones with hydroxy azides and the application of the intramolecular Schmidt reaction toward the total synthesis of lasubines I and II /Vijaya Judith Gracias. - 1 electronic resource (183 pages)

Source: Dissertations Abstracts International, Volume: 60-06, Section: B.

This dissertation describes the intermolecular Schmidt reaction of hydroxy azides with ketones, the development of an asymmetric version of this reaction and the application of the intramolecular Schmidt reaction toward the total synthesis of lasubines I and II. For many years the Schmidt reaction of ketones was limited to the use of hydrazoic acid as the azide component. In previous work Aube and coworkers extended the Schmidt reaction to permit simple alkyl azides to react with ketones providing a direct route to N-alkyl substituted lactams. In this dissertation, the further extension of this reaction to incorporate hydroxy azides in lieu of alkyl azides to afford N-hydroxyalkyl lactams is described. The intermediacy of isolable and stable iminium ethers was also demonstrated. The ambident electrophilicity of these intermediates was exploited by incorporating different nucleophiles on the ring system. Finally, the first example of an asymmetric Schmidt reaction was demonstrated by carrying out the reaction of a chiral hydroxy azide and a prochiral ketone. The application of the intramolecular Schmidt reaction toward the total synthesis of lasubines I and II is also described. In course of this investigation, we have demonstrated the stereoselective synthesis of a key keto azide derived from 4-hydroxy-2-cyclopentenone (183). The intramolecular Schmidt reaction of this keto azide proceeded as expected, but the stereoselectivity of the process was poor on account of epimerization of the center $\\alpha$ to the carbonyl under the conditions employed. Of particular note was the development of a method to generate (4S)-($-$)-4-triisopropylsilyloxy-2-cyclopenten-1-one (209) in an asymmetric fashion in good yields. Preliminary Grignard reactions on several advanced intermediates were presented; one of these afforded a total synthesis of 4-ent-epi-lasubine I.

English

ISBN: 9780599021181Subjects--Topical Terms:

634543
Pharmacology.
Subjects--Index Terms:

Hydroxy azides

New reactions of ketones with hydroxy azides and the application of the intramolecular Schmidt reaction toward the total synthesis of lasubines I and II /
LDR:03198nmm a22003853i 4500 001 2428821
005 20250414022034.5
006 m o d
007 cr|nu||||||||
008 261011s1998 miu||||||m |||||||eng d
020 $a 9780599021181
035 $a (MiAaPQD)AAI9904804
035 $a AAI9904804
040 $a MiAaPQD $b eng $c MiAaPQD $e rda
100 1 $a Gracias, Vijaya Judith, $e author. $3 3816275
245 1 0 $a New reactions of ketones with hydroxy azides and the application of the intramolecular Schmidt reaction toward the total synthesis of lasubines I and II / $c Vijaya Judith Gracias.
264 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 1998
300 $a 1 electronic resource (183 pages)
336 $a text $b txt $2 rdacontent
337 $a computer $b c $2 rdamedia
338 $a online resource $b cr $2 rdacarrier
500 $a Source: Dissertations Abstracts International, Volume: 60-06, Section: B.
500 $a Publisher info.: Dissertation/Thesis.
502 $b Ph.D. $c University of Kansas $d 1998.
520 $a This dissertation describes the intermolecular Schmidt reaction of hydroxy azides with ketones, the development of an asymmetric version of this reaction and the application of the intramolecular Schmidt reaction toward the total synthesis of lasubines I and II. For many years the Schmidt reaction of ketones was limited to the use of hydrazoic acid as the azide component. In previous work Aube and coworkers extended the Schmidt reaction to permit simple alkyl azides to react with ketones providing a direct route to N-alkyl substituted lactams. In this dissertation, the further extension of this reaction to incorporate hydroxy azides in lieu of alkyl azides to afford N-hydroxyalkyl lactams is described. The intermediacy of isolable and stable iminium ethers was also demonstrated. The ambident electrophilicity of these intermediates was exploited by incorporating different nucleophiles on the ring system. Finally, the first example of an asymmetric Schmidt reaction was demonstrated by carrying out the reaction of a chiral hydroxy azide and a prochiral ketone. The application of the intramolecular Schmidt reaction toward the total synthesis of lasubines I and II is also described. In course of this investigation, we have demonstrated the stereoselective synthesis of a key keto azide derived from 4-hydroxy-2-cyclopentenone (183). The intramolecular Schmidt reaction of this keto azide proceeded as expected, but the stereoselectivity of the process was poor on account of epimerization of the center $\\alpha$ to the carbonyl under the conditions employed. Of particular note was the development of a method to generate (4S)-($-$)-4-triisopropylsilyloxy-2-cyclopenten-1-one (209) in an asymmetric fashion in good yields. Preliminary Grignard reactions on several advanced intermediates were presented; one of these afforded a total synthesis of 4-ent-epi-lasubine I.
546 $a English
590 $a School code: 0099
650 4 $a Pharmacology. $3 634543
650 4 $a Organic chemistry. $3 523952
653 $a Hydroxy azides
653 $a Ketones
653 $a Lactams
653 $a Lasubines
690 $a 0490
710 2 $a University of Kansas. $e degree granting institution. $3 3816276
773 0 $t Dissertations Abstracts International $g 60-06B.
790 $a 0099
791 $a Ph.D.
792 $a 1998
856 4 0 $u https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9904804