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Application of chiral bis(phosphine)...

Wilt, Jeremy Clinton.

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Application of chiral bis(phosphine) monosulfide ligands to palladium-catalyzed asymmetric allylic alkylation.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Application of chiral bis(phosphine) monosulfide ligands to palladium-catalyzed asymmetric allylic alkylation./
Author:	Wilt, Jeremy Clinton.
Description:	222 p.
Notes:	Source: Dissertation Abstracts International, Volume: 66-11, Section: B, page: 5978.
Contained By:	Dissertation Abstracts International66-11B.
Subject:	Chemistry, Inorganic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3194725
ISBN:	9780542395055

Application of chiral bis(phosphine) monosulfide ligands to palladium-catalyzed asymmetric allylic alkylation.
Wilt, Jeremy Clinton.

Application of chiral bis(phosphine) monosulfide ligands to palladium-catalyzed asymmetric allylic alkylation. - 222 p.

Source: Dissertation Abstracts International, Volume: 66-11, Section: B, page: 5978.

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

The chiral bis(phosphine) monosulfide ligand (S)-BINAP(S) and its corresponding [(eta3-allyl)Pd(S-BINAP(S))]SbF 6 complex were synthesized and the Pd complex was used in the kinetic resolution of allylic acetates and benzoates in the course of the Pd-catalyzed asymmetric allylic alkylation reaction with sodium dimethylmalonate as the nucleophile. Very high S values (8.5-26) were observed for the kinetic resolution process; additionally, an unusual regioselectivity was noted when using unsymmetrically substituted allylic substrates, favoring the branched regioisomeric product.

ISBN: 9780542395055Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Application of chiral bis(phosphine) monosulfide ligands to palladium-catalyzed asymmetric allylic alkylation.
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035 $a (UnM)AAI3194725
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100 1 $a Wilt, Jeremy Clinton. $3 1917056
245 1 0 $a Application of chiral bis(phosphine) monosulfide ligands to palladium-catalyzed asymmetric allylic alkylation.
300 $a 222 p.
500 $a Source: Dissertation Abstracts International, Volume: 66-11, Section: B, page: 5978.
500 $a Director: J. W. Faller.
502 $a Thesis (Ph.D.)--Yale University, 2005.
520 $a The chiral bis(phosphine) monosulfide ligand (S)-BINAP(S) and its corresponding [(eta3-allyl)Pd(S-BINAP(S))]SbF 6 complex were synthesized and the Pd complex was used in the kinetic resolution of allylic acetates and benzoates in the course of the Pd-catalyzed asymmetric allylic alkylation reaction with sodium dimethylmalonate as the nucleophile. Very high S values (8.5-26) were observed for the kinetic resolution process; additionally, an unusual regioselectivity was noted when using unsymmetrically substituted allylic substrates, favoring the branched regioisomeric product.
520 $a The above catalytic system was also applied to the asymmetric synthesis of acyclic allylic esters by using a bulky carboxylate nucleophile, which proceeded in high ee (up to 90%). Additionally, a highly selective kinetic resolution was observed when using a 1,3-dimethylallyl substrate ( S = 38). Branched regioisomeric products were obtained with very high regioselectivity (>90%), which is highly unusual.
520 $a Asymmetric allylic amination was also attempted with the aforementioned catalytic system. Excellent enantioselectivities (many > 88%) were observed; the trend of producing the chiral, branched regioisomeric product continued in this study. Modification of the parent (S)-BINAP(S) ligand was found to increase the enantioselectivity of the reaction. X-ray crystallographic data confirmed the binding mode of the (S)-BINAP(S) ligand to be kappa2-P,S in the solid state.
520 $a A detailed look into the factors contributing to the observed unusual regioselectivity was undertaken in the context of Pd-catalyzed allylic amination. Numerous unsymmetrically substituted allylic substrates were screened. Solid-state and solution analyses of several unsymmetrically substituted [(eta 3-allyl)Pd((S)-BINAP(S)]SbF6 compounds were performed. Spin-saturation transfer 1H NMR experiments were performed in order to elucidate the dynamic behavior of two [(eta 3-allyl)Pd(kappa2-P,S)]SbF 6 compounds in solution. The hemilability of the P,S ligands was revealed.
520 $a A successful resolution of the axially chiral BIPHEP ligand on Rh was achieved with the aid of a chiral diene auxiliary ligand. Polarimetry measurements allowed for the determination of DeltaG&Dagger; for the BIPHEP ligand on Rh.
590 $a School code: 0265.
650 4 $a Chemistry, Inorganic. $3 517253
690 $a 0488
710 2 0 $a Yale University. $3 515640
773 0 $t Dissertation Abstracts International $g 66-11B.
790 1 0 $a Faller, J. W., $e advisor
790 $a 0265
791 $a Ph.D.
792 $a 2005
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3194725