کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1345371 980194 2007 14 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
An asymmetric synthesis of carboxylic acid derivatives, including lactic acid and α-amino acid derivatives, from optically active 1-chlorovinyl p-tolyl sulfoxides and ester lithium enolates with creation of chirality at the α-position
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
An asymmetric synthesis of carboxylic acid derivatives, including lactic acid and α-amino acid derivatives, from optically active 1-chlorovinyl p-tolyl sulfoxides and ester lithium enolates with creation of chirality at the α-position
چکیده انگلیسی

Treatment of optically active 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from symmetrical ketones or methyl formate and (R)-(−)-chloromethyl p-tolyl sulfoxide in three steps, with lithium enolate of carboxylic acid tert-butyl esters gave optically active adducts having a substituent (alkyl, alkoxy, or dibenzylamino group) at the α-position with high 1,4-chiral induction from the sulfur chiral center. The adducts were converted to optically active esters, lactic acid, and α-amino acid derivatives having a chiral center at the α-position. When this addition reaction was carried out with an ester enolate generated from excess carboxylic acid tert-butyl ester with LDA in the presence of HMPA, the diastereomer of the adduct was obtained. By using the two reaction conditions for the generation of the ester enolate, a new method for asymmetric synthesis of both enantiomers of carboxylic acid derivatives having a substituent at the α-position from the one chiral source, (R)-(−)-chloromethyl p-tolyl sulfoxide, was achieved.

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(R)-1-Chloro-2-methyl-1-(p-tolylsulfinyl)-1-propeneC11H13ClOSEe = 99%[α]D24=+156.2 (c 1.0, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(R)-[Chloro-(p-tolylsulfiny)methylidene]cyclohexaneC14H17ClOSEe = 99%[α]D25=+213.0 (c 1.0, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(R)-[Chloro-(p-tolylsulfinyl)methylidene]cyclopentadecaneC22H35ClOSEe = 99%[α]D24=+120.7 (c 1.3, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(R)-1-Chloroethenyl p-tolyl sulfoxideC9H9ClOSEe = 99%[α]D25=+151.4 (c 0.8, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(2R)-(−)-tert-Butyl 2,3,3-trimethyl-4-(p-tolylsulfonyl)butanoateC18H28O4SEe = 96%[α]D30=-14.3 (c 1.2, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(2R)-(−)-tert-Butyl 2-{1-[(p-tolylsulfonyl)methyl]cyclohexy}propionateC21H32O4SEe = 97%[α]D26=-5.3 (c 1.8, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(2R)-(−)-tert-Butyl 2-{1-[(p-tolylsulfonyl)methyl]cyclopentadecyl}propionateC30H50O4SEe = 97%[α]D24=-4.3 (c 0.9, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(2R)-(−)-tert-Butyl 2-ethyl-3,3-dimethyl-4-(p-tolylsulfonyl)butanoateC19H30O4SEe = 93%[α]D26=-3.0 (c 1.7, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(2R)-(−)-tert-Butyl 2-{1-[(p-tolylsulfonyl)methyl]cyclohexyl}butanoateC22H34O4SEe = 99%[α]D26=-4.9 (c 1.8, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(2R)-(−)-tert-Butyl 2-{1-[(p-tolylsulfonyl)methyl]cyclopentadecyl}butanoateC31H52O4SEe = 97%[α]D26=-1.7 (c 0.9, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(2R)-(−)-tert-Butyl 2-[1,1-dimethyl-2-(p-tolylsulfonyl)ethyl]hexanoateC21H34O4SEe = 96%[α]D28=-0.5 (c 2.8, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(2R)-(−)-tert-Butyl 2-{1-[(p-tolylsulfonyl)methyl]cyclopentadecyl}hexanoateC33H56O4SEe = 97%[α]D27=-1.9 (c 0.9, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(R)-(−)-2,3,3-Trimethylbutyric acidC7H14O2Ee = 96%[α]D28=-20.8 (c 0.7, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(R)-(+)-3-Benzyloxy-4,4-dimethyldihydrofuran-2-oneC13H16O3Ee = 99%[α]D28=+112.5 (c 0.22, CHCl3)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(R)-(+)-4-Benzyloxy-2-oxaspiro[4.5]decan-3-oneC16H20O3Ee = 97%[α]D27=+101.2 (c 0.91, CHCl3)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(R)-(+)-3-Dibenzylaminodihydrofuran-2-oneC18H19NO2Ee = 87%[α]D28=+26.5 (c 0.22, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(R)-(+)-3-Dibenzylamino-4,4-dimethyldihydrofuran-2-oneC20H23NO2Ee = 99%[α]D29=+137 (c 0.47, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(R)-(+)-4-Dibenzylamino-2-oxaspiro[4.5]decan-3-oneC23H27NO2Ee = 99%[α]D27=+91.5 (c 1.0, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(R)-(−)-(4,4-Dimethyl-2-oxotetrahydrofuran-3-yl)carbamic acid methyl esterC8H13NO4Ee = 99%[α]D28=-8.2 (c 1.0, CHCl3)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (R)

(2S)-(+)-tert-Butyl 2-{1-[(p-tolylsulfonyl)methyl]cyclopentadecyl}propionateC30H50O4SEe = 99%[α]D23=+5.05 (c 1.34, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (S)

(2S)-(+)-tert-Butyl 2-{1-[(p-tolylsulfonyl)methyl]cyclopentadecyl}butanoateC31H52O4SEe = 99%[α]D25=+1.75 (c 0.45, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (S)

(2S)-(+)-tert-Butyl 2,3,3-trimethyl-4-(p-tolysulfonyl)butanoateC18H28O4SEe = 80%[α]D28=+9.8 (c 0.84, ethanol)Source of chirality: (R)-(−)-chloromethyl p-tolyl sulfoxideAbsolute configuration: (S)

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Tetrahedron: Asymmetry - Volume 18, Issue 16, 22 August 2007, Pages 1934–1947
نویسندگان
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