國立高雄大學圖資館 |

Language: English

Back

The diastereoselective Pauson-Khand ...

Miller, Stefan Michael.

The diastereoselective Pauson-Khand cyclization of nitrogen-oxygen, nitrogen-nitrogen tethered enynes and progress towards the synthesis of the axinellamines.

Record Type:	Electronic resources : Monograph/item
Title/Author:	The diastereoselective Pauson-Khand cyclization of nitrogen-oxygen, nitrogen-nitrogen tethered enynes and progress towards the synthesis of the axinellamines.
Author:	Miller, Stefan Michael.
Description:	339 p.
Notes:	Director: David Joseph Austin.
Notes:	Source: Dissertation Abstracts International, Volume: 66-11, Section: B, page: 5987.
Contained By:	Dissertation Abstracts International66-11B.
Subject:	Chemistry, Organic.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3194689
ISBN:	9780542394911

The diastereoselective Pauson-Khand cyclization of nitrogen-oxygen, nitrogen-nitrogen tethered enynes and progress towards the synthesis of the axinellamines.
Miller, Stefan Michael.

The diastereoselective Pauson-Khand cyclization of nitrogen-oxygen, nitrogen-nitrogen tethered enynes and progress towards the synthesis of the axinellamines. - 339 p.

Director: David Joseph Austin.

Thesis (Ph.D.)--Yale University, 2005.

The Pauson-Khand cyclization is performed on transiently N-O or N-N tethered enyne systems yielding bicyclic cyclopentenones in a diastereoselective manner with the core structural features of several bisguanidine alkaloids including the palau'amines, styloguanidines, and axinellamines. Enynes containing a stereodefined allylic group are readily formed from the chiral synthon D-Mannitol and promotion of the cyclization reaction is achieved with an improved TMANO (trimethylamine N-oxide), NMO (N-methyl morpholine), or alkyl-sulfide/DMSO promoted induction sequence. A methodological study of numerous promotion conditions is provided detailing the effects of alternate promoters, solvent, temperature, and atmosphere on variously substituted N-O and N-N enynes. Furthermore, we demonstrate the ability of protection at the N-O, N-N site to promote the Pauson-Khand cyclization on unstrained disubstituted olefins. Ensuing cleavage of the tether provides a cyclopentane core with pendant orthogonally reactive functionality for further modification. In addition, the asymmetric Pauson-Khand is utilized for formation of the core ring of axinellamine absent a chiral auxillary, providing product in good yield with moderate enantioselectivities. Model systems are described for utilizing the asymmetric Pauson-Khand cyclization for the expedient synthesis of the axinellamines.

ISBN: 9780542394911Subjects--Topical Terms:

193634
Chemistry, Organic.

The diastereoselective Pauson-Khand cyclization of nitrogen-oxygen, nitrogen-nitrogen tethered enynes and progress towards the synthesis of the axinellamines.
LDR:02403nmm _2200253 _450 001 170948
005 20061228142328.5
008 090528s2005 eng d
020 $a 9780542394911
035 $a 00242978
040 $a UnM $c UnM
100 0 $a Miller, Stefan Michael. $3 244979
245 1 4 $a The diastereoselective Pauson-Khand cyclization of nitrogen-oxygen, nitrogen-nitrogen tethered enynes and progress towards the synthesis of the axinellamines.
300 $a 339 p.
500 $a Director: David Joseph Austin.
500 $a Source: Dissertation Abstracts International, Volume: 66-11, Section: B, page: 5987.
502 $a Thesis (Ph.D.)--Yale University, 2005.
520 # $a The Pauson-Khand cyclization is performed on transiently N-O or N-N tethered enyne systems yielding bicyclic cyclopentenones in a diastereoselective manner with the core structural features of several bisguanidine alkaloids including the palau'amines, styloguanidines, and axinellamines. Enynes containing a stereodefined allylic group are readily formed from the chiral synthon D-Mannitol and promotion of the cyclization reaction is achieved with an improved TMANO (trimethylamine N-oxide), NMO (N-methyl morpholine), or alkyl-sulfide/DMSO promoted induction sequence. A methodological study of numerous promotion conditions is provided detailing the effects of alternate promoters, solvent, temperature, and atmosphere on variously substituted N-O and N-N enynes. Furthermore, we demonstrate the ability of protection at the N-O, N-N site to promote the Pauson-Khand cyclization on unstrained disubstituted olefins. Ensuing cleavage of the tether provides a cyclopentane core with pendant orthogonally reactive functionality for further modification. In addition, the asymmetric Pauson-Khand is utilized for formation of the core ring of axinellamine absent a chiral auxillary, providing product in good yield with moderate enantioselectivities. Model systems are described for utilizing the asymmetric Pauson-Khand cyclization for the expedient synthesis of the axinellamines.
590 $a School code: 0265.
650 # 0 $a Chemistry, Organic. $3 193634
690 $a 0490
710 0 # $a Yale University. $3 212430
773 0 # $g 66-11B. $t Dissertation Abstracts International
790 $a 0265
790 1 0 $a Austin, David Joseph, $e advisor
791 $a Ph.D.
792 $a 2005
856 4 0 $u http://libsw.nuk.edu.tw:81/login?url=http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3194689 $z http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3194689