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Design and development of transition metal-catalyzed [M+N] cycloadditions :New methods for the synthesis of medium-sized ring systems and synthetic studies on gnidimacrin :

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Design and development of transition metal-catalyzed [M+N] cycloadditions :
其他題名:	New methods for the synthesis of medium-sized ring systems and synthetic studies on gnidimacrin :
作者:	Sun, Robert.
面頁冊數:	492 p.
附註:	Adviser: Paul A. Wender.
附註:	Source: Dissertation Abstracts International, Volume: 65-04, Section: B, page: 1875.
Contained By:	Dissertation Abstracts International65-04B.
標題:	Chemistry, Organic.
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3128693
ISBN:	0496759558

Design and development of transition metal-catalyzed [M+N] cycloadditions :New methods for the synthesis of medium-sized ring systems and synthetic studies on gnidimacrin :
Sun, Robert.

Design and development of transition metal-catalyzed [M+N] cycloadditions :New methods for the synthesis of medium-sized ring systems and synthetic studies on gnidimacrin :[electronic resource] - 492 p.

Adviser: Paul A. Wender.

Thesis (Ph.D.)--Stanford University, 2004.

Another focus in the Wender group involves the synthesis of structurally novel polycyclic natural products with unique biological activity. Report herein is a concise and flexible macrolactonization approach towards the synthesis of gnidimacrin. The synthesis of the ABC tricyclic core of gnidimacrin is achieved in 20 sequential steps from commercially available acrolein (24 overall steps). Key reactions include a room temperature oxidopyrylium [5+2] cycloaddition to construct the BC ring system, a 1,2-addition reaction to introduce the side-chain of gnidimacrin, and a complex "ligandless" palladium-catalyzed reductive enyne cyclization to furnish the ABC core structure.

ISBN: 0496759558Subjects--Topical Terms:

193634
Chemistry, Organic.

Design and development of transition metal-catalyzed [M+N] cycloadditions :New methods for the synthesis of medium-sized ring systems and synthetic studies on gnidimacrin :
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245 1 0 $a Design and development of transition metal-catalyzed [M+N] cycloadditions : $b New methods for the synthesis of medium-sized ring systems and synthetic studies on gnidimacrin : $b A general approach to the 1-alkyldaphnanes $h [electronic resource]
300 $a 492 p.
500 $a Adviser: Paul A. Wender.
500 $a Source: Dissertation Abstracts International, Volume: 65-04, Section: B, page: 1875.
502 $a Thesis (Ph.D.)--Stanford University, 2004.
520 # $a Another focus in the Wender group involves the synthesis of structurally novel polycyclic natural products with unique biological activity. Report herein is a concise and flexible macrolactonization approach towards the synthesis of gnidimacrin. The synthesis of the ABC tricyclic core of gnidimacrin is achieved in 20 sequential steps from commercially available acrolein (24 overall steps). Key reactions include a room temperature oxidopyrylium [5+2] cycloaddition to construct the BC ring system, a 1,2-addition reaction to introduce the side-chain of gnidimacrin, and a complex "ligandless" palladium-catalyzed reductive enyne cyclization to furnish the ABC core structure.
520 # $a From the ABC ring system, the appendage of the alkyl side-chain of gnidimacrin is successfully achieved. Additionally, utilizing a high yielding oxo-bridge cleavage and a stereoselective opening of an alpha epoxide, the synthesis of a macrolactone precursor is reported in 34 steps from commercially available starting material.
520 # $a In contrast, the analogous rhodium-catalyzed cycloaddition of less strained allenyl ethers with CO led to the discovery of a novel rhodium(I)-catalyzed carbonylative rearrangement reaction to form a variety of lactones. Of mechanistic significance is the selective activation of a C-O bond over a C-C bond in these unstrained systems. Preliminary results are also described.
520 # $a Preliminary investigation into the intermolecular [6+2] cycloadditions led to the discovery of a metal-catalyzed C-C bond activation in an allenylcyclobutyl ether moiety. The efficiency of this catalytic process is demonstrated through the first examples of a transition metal-catalyzed [6+1] cycloaddition of allenylcyclobutyl ethers with CO, a new approach to seven-membered rings.
520 # $a The design and the development of a rhodium(I)-catalyzed intramolecular [6+2] cycloaddition of 2-vinylcyclobutanone with alkenes to form eight-membered rings is described. The scope and generality of this cycloaddition is investigated with respect to solvent effects, catalyst type, tether atoms (C-, N-, and O-linked systems), substitution of the alkene, and the utility of an allene.
590 $a School code: 0212.
650 # 0 $a Chemistry, Organic. $3 193634
690 $a 0490
710 0 # $a Stanford University. $3 212607
773 0 # $g 65-04B. $t Dissertation Abstracts International
790 $a 0212
790 1 0 $a Wender, Paul A., $e advisor
791 $a Ph.D.
792 $a 2004
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