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Asymmetric transformations of C=O an...

Huang, Gang.

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Asymmetric transformations of C=O and C=C double bonds to chiral alcohols using chiral auxiliaries and catalysts.

Record Type:	Language materials, printed : Monograph/item
Title/Author:	Asymmetric transformations of C=O and C=C double bonds to chiral alcohols using chiral auxiliaries and catalysts./
Author:	Huang, Gang.
Description:	145 p.
Notes:	Adviser: Rawle I. Hollingsworth.
Contained By:	Dissertation Abstracts International61-02B.
Subject:	Chemistry, Organic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9963345
ISBN:	9780599677418

Asymmetric transformations of C=O and C=C double bonds to chiral alcohols using chiral auxiliaries and catalysts.
Huang, Gang.

Asymmetric transformations of C=O and C=C double bonds to chiral alcohols using chiral auxiliaries and catalysts. - 145 p.

Adviser: Rawle I. Hollingsworth.

Thesis (Ph.D.)--Michigan State University, 1999.

The asymmetric transformation of C=C and C=O double bond to chiral alcohols using several readily available chiral molecules as chiral auxiliaries or phase-transfer catalysts was investigated. In a key step, 2-OH of a D-glucose unit (chiral auxiliary) was used as an intramolecular nucleophile for the oxymercuration of 2-alkenyl glucosides with high to excellent stereochemical control. The absolute configuration of the new chiral center was determined by which anomer (alpha or beta) to start with. After removal of the auxiliary, pure (R)- or (S)-alkane-1, 2-diols and other chiral intermediates were retrieved. The chiral 1,2-diols were also synthesized with good stereoselectivity via chiral reduction of alpha-hydroxy ketones using D-glucose as the chiral auxiliary. The configuration of starting anomer also determined the chirality of the major isomer. The complexation with calcium (II) played an important role in the chiral induction. The use of hexadecyl nicotinium iodide as a phase transfer catalyst for stereoselective reduction of 3-keto fatty acids was also investigated, which only gave low enantioselectivity. The stereoselective reduction of benzoyl formic acid to mandelic acid using nicotine as a complexing reagent was also attempted and low to fair chiral induction was observed. In general, nicotine as we employed it here is not a good chiral auxiliary for asymmetric reduction due to its structural flexibility. The reductive cleavage of 3,4-dihydro-1(2H)-naphthalenespiro-2-(5' -methyl-1',3'-dioxolan-4 '-one) formed from (L)-lactic acid was achieved with good stereoselectivity by using a combination of chlorotrimethylsilane, zinc borohydride and lutidine. The optical purity of starting dioxolanone had no effect on the stereochemical outcome of the product. The lactic acid unit was later removed successfully, but racemization of 1,2,3,4-tetrahydro-1-naphthol was observed. The investigation had shed some lights on the synthesis of chiral alcohols using lactic acid as a chiral auxiliary.

ISBN: 9780599677418Subjects--Topical Terms:

516206
Chemistry, Organic.

Asymmetric transformations of C=O and C=C double bonds to chiral alcohols using chiral auxiliaries and catalysts.
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100 1 $a Huang, Gang. $3 1258038
245 1 0 $a Asymmetric transformations of C=O and C=C double bonds to chiral alcohols using chiral auxiliaries and catalysts.
300 $a 145 p.
500 $a Adviser: Rawle I. Hollingsworth.
500 $a Source: Dissertation Abstracts International, Volume: 61-02, Section: B, page: 0856.
502 $a Thesis (Ph.D.)--Michigan State University, 1999.
520 $a The asymmetric transformation of C=C and C=O double bond to chiral alcohols using several readily available chiral molecules as chiral auxiliaries or phase-transfer catalysts was investigated. In a key step, 2-OH of a D-glucose unit (chiral auxiliary) was used as an intramolecular nucleophile for the oxymercuration of 2-alkenyl glucosides with high to excellent stereochemical control. The absolute configuration of the new chiral center was determined by which anomer (alpha or beta) to start with. After removal of the auxiliary, pure (R)- or (S)-alkane-1, 2-diols and other chiral intermediates were retrieved. The chiral 1,2-diols were also synthesized with good stereoselectivity via chiral reduction of alpha-hydroxy ketones using D-glucose as the chiral auxiliary. The configuration of starting anomer also determined the chirality of the major isomer. The complexation with calcium (II) played an important role in the chiral induction. The use of hexadecyl nicotinium iodide as a phase transfer catalyst for stereoselective reduction of 3-keto fatty acids was also investigated, which only gave low enantioselectivity. The stereoselective reduction of benzoyl formic acid to mandelic acid using nicotine as a complexing reagent was also attempted and low to fair chiral induction was observed. In general, nicotine as we employed it here is not a good chiral auxiliary for asymmetric reduction due to its structural flexibility. The reductive cleavage of 3,4-dihydro-1(2H)-naphthalenespiro-2-(5' -methyl-1',3'-dioxolan-4 '-one) formed from (L)-lactic acid was achieved with good stereoselectivity by using a combination of chlorotrimethylsilane, zinc borohydride and lutidine. The optical purity of starting dioxolanone had no effect on the stereochemical outcome of the product. The lactic acid unit was later removed successfully, but racemization of 1,2,3,4-tetrahydro-1-naphthol was observed. The investigation had shed some lights on the synthesis of chiral alcohols using lactic acid as a chiral auxiliary.
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710 2 0 $a Michigan State University. $3 676168
773 0 $t Dissertation Abstracts International $g 61-02B.
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791 $a Ph.D.
792 $a 1999
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9963345