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Multicomponent linchpin couplings. Reaction of dithiane anions with terminal epoxides, aziridines and vinyl epoxides :Efficient, rapid and stereocontrolled assembly of advanced fragments for complex molecule synthesis.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Multicomponent linchpin couplings. Reaction of dithiane anions with terminal epoxides, aziridines and vinyl epoxides :
Reminder of title:	Efficient, rapid and stereocontrolled assembly of advanced fragments for complex molecule synthesis.
Author:	Pitram, Suresh Mark.
Description:	464 p.
Notes:	Source: Dissertation Abstracts International, Volume: 64-10, Section: B, page: 4948.
Notes:	Supervisor: Amos B. Smith, III.
Contained By:	Dissertation Abstracts International64-10B.
Subject:	Chemistry, Organic.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3109211
ISBN:	0496567543

Multicomponent linchpin couplings. Reaction of dithiane anions with terminal epoxides, aziridines and vinyl epoxides :Efficient, rapid and stereocontrolled assembly of advanced fragments for complex molecule synthesis.
Pitram, Suresh Mark.

Multicomponent linchpin couplings. Reaction of dithiane anions with terminal epoxides, aziridines and vinyl epoxides :Efficient, rapid and stereocontrolled assembly of advanced fragments for complex molecule synthesis. [electronic resource] - 464 p.

Source: Dissertation Abstracts International, Volume: 64-10, Section: B, page: 4948.

Thesis (Ph.D.)--University of Pennsylvania, 2003.

The development and application of a one-flask, multicomponent linchpin coupling protocol of 2-silyl-1,3-dithianes with epoxides exploiting a solvent controlled Brook rearrangement (C → O silyl migration) is described in Chapter 1. Also presented are the advantages of this tactic over the more conventional step-wise addition of dithiane anions to electrophiles. The second chapter details further applications and extension of this tactic. A one-flask, five-component coupling is employed in the synthesis of the extended 1,3-polyol moiety prevalent in the oxopolyene macrolides mycoticins A and B. An investigation of 2-silyl-1,3-dithiane additions to nitrogen-containing electrophiles (i.e., aziridines, nitrites, imines and nitrones) and the corresponding aza-Brook rearrangement (C → N silyl migration) are conducted. In addition, vinyl epoxides prove to be competent electrophiles for dithiane additions exhibiting high chemoselectivity between the SN2 and SN2 ' reaction manifolds. The steric nature of the dithiane anion is critical; sterically unencumbered dithiane anions afford SN2 adducts, whereas encumbered anions lead primarily to SN2 ' adducts. Mechanistic studies demonstrate that the SN 2' process occurs via syn addition to the vinyl epoxide. By utilizing this reaction and the one-flask, three-component coupling, the C(1--18) polyol segment of rimodicin is prepared. Integration of epihalohydrins and vinyl epoxides leads to a novel electrophile permitting the higher-order multicomponent union of four and five components.

ISBN: 0496567543Subjects--Topical Terms:

193634
Chemistry, Organic.

Multicomponent linchpin couplings. Reaction of dithiane anions with terminal epoxides, aziridines and vinyl epoxides :Efficient, rapid and stereocontrolled assembly of advanced fragments for complex molecule synthesis.
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