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Asymmetric formation of "chiral aldehyde" equivalents :Applications in organic synthesis.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Asymmetric formation of "chiral aldehyde" equivalents :
Reminder of title:	Applications in organic synthesis.
Author:	Crawley, Matthew Lantz.
Description:	453 p.
Notes:	Adviser: Barry M. Trost.
Notes:	Source: Dissertation Abstracts International, Volume: 64-05, Section: B, page: 2189.
Contained By:	Dissertation Abstracts International64-05B.
Subject:	Chemistry, Organic.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3090574
ISBN:	0496382969

Asymmetric formation of "chiral aldehyde" equivalents :Applications in organic synthesis.
Crawley, Matthew Lantz.

Asymmetric formation of "chiral aldehyde" equivalents :Applications in organic synthesis. [electronic resource] - 453 p.

Adviser: Barry M. Trost.

Thesis (Ph.D.)--Stanford University, 2003.

Chiral gamma-acyloxybutenolides, readily accessible through a dynamic kinetic asymmetric transformation (DYKAT) of racemic acyloxybutenolides, were utilized as "chiral aldehyde" building blocks for intermolecular Michael reactions and cycloadditions. Unprecedented selectivity in TMM cycloadditions with this butenolide building block allowed for efficient synthesis of an active Bayer compound. These studies inspired work that culminated in the total synthesis of (+)-brefeldin A, a natural product with significant biological properties. All of the stereochemistry in the molecule was derived from two AAA reactions. The trans-alkenes were established by a Julia olefination and a ruthenium-catalyzed trans-hydrosilylation-protodesilylation protocol. This route to (+)-brefeldin A lends itself to analogue syntheses and was completed in 18 steps in 6% overall yield.

ISBN: 0496382969Subjects--Topical Terms:

193634
Chemistry, Organic.

Asymmetric formation of "chiral aldehyde" equivalents :Applications in organic synthesis.
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245 1 0 $a Asymmetric formation of "chiral aldehyde" equivalents : $b Applications in organic synthesis. $h [electronic resource]
300 $a 453 p.
500 $a Adviser: Barry M. Trost.
500 $a Source: Dissertation Abstracts International, Volume: 64-05, Section: B, page: 2189.
502 $a Thesis (Ph.D.)--Stanford University, 2003.
520 # $a Chiral gamma-acyloxybutenolides, readily accessible through a dynamic kinetic asymmetric transformation (DYKAT) of racemic acyloxybutenolides, were utilized as "chiral aldehyde" building blocks for intermolecular Michael reactions and cycloadditions. Unprecedented selectivity in TMM cycloadditions with this butenolide building block allowed for efficient synthesis of an active Bayer compound. These studies inspired work that culminated in the total synthesis of (+)-brefeldin A, a natural product with significant biological properties. All of the stereochemistry in the molecule was derived from two AAA reactions. The trans-alkenes were established by a Julia olefination and a ruthenium-catalyzed trans-hydrosilylation-protodesilylation protocol. This route to (+)-brefeldin A lends itself to analogue syntheses and was completed in 18 steps in 6% overall yield.
520 # $a Palladium-catalyzed asymmetric allylic alkylations (AAA) to form "chiral aldehyde" equivalents were investigated. alpha-Acetoxysulfones formed in high enantiomeric excess as single regioisomers in AAA reactions of allylic geminal dicarboxylates with sodium benzenesulfinate. The directing ability of this novel functional group was highlighted in a series of dihydroxylations, affording diols as single diastereomers in excellent yields. This was the first example of an asymmetric dihydroxylation protocol that gives the equivalent of reaction with a simple enal. The value of this process was exemplified by development of a one pot dihydroxylation-deprotective acyl migration protocol to give differentially protected 1,2-diols.
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