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One-Pot Synthesis Of Chiral Disulfides & Diselenides From α-Amino Acids Mediated By Ammonium Tetrathiomolybdate In Water

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Title One-Pot Synthesis Of Chiral Disulfides & Diselenides From α-Amino Acids Mediated By Ammonium Tetrathiomolybdate In Water
 
Creator Navin, V
 
Subject Organic Chemistry
Tetrathiomolybdate
Sulfur Compounds
Amino Acids
Carboxylic Acids
Selinide Compounds
Sulfur Transfer
Thiocyanate
Reductive Dimerization
Selenocyante
Thiocyanato Carboxylic Acids
Disulfides
Diselenides
 
Description We have described herein a convenient one-pot synthesis of lisulfides/diselenides from a-amino acids mediated by ammonium etrathiomolybdate in water. (Figure 1)
(Figure)
Figure 1 Transformation of α-amino acids into the corresponding tiiocyanates/selenocyanates/disulfides/diselenides

Halo-de-amination of a-amino acids using HBr/NaNCte followed by treatment with ammonium tetrathiomolybdate (NH4)2]VloS4 jLb provided a general route for the the one-pot synthesis of chiral a,a' bis (dithio) carboxylic acids (Figure 1, 2b). The yields were moderate, limited mainly the moderate conversion of a-amino acids into the corresponding chiral a-bromides.

It was possible to synthesize the 2-thiocyanto carboxylic acids from the corresponding a-amino acids by a similar strategy. Thus diazotization in the presence of KSCN yielded in the chiral 2-thiocyanto carboxylic acids in moderate yields (Figure 1, 3). Thiocyanato-de-amination thus afforded the thiocyanates which when treated with JJD provided the chiral disulfides (Figure 1, 4a). We could thus synthesize both enantiomers of the disulfide from a single enantiomer of the starting a-amino acid. (Figure 1, 4a,4b)
Using a similar strategy we have also demonstrated an efficient method for the synthesis of chiral selenocyanates starting from a-amino acids, using selenocyanate anion as the nucleophile (Figure 1, 5). It is possible to demonstrate a one-pot synthesis of chiral diselenides by reductive coupling of selenocyanates using JJb. (Figure 1, 6)
(for figure see the pdf file)
 
Publisher Indian Institute of Science
 
Contributor Chandrasekaran, Srinivasan
 
Date 2007-03-27T04:16:47Z
2007-03-27T04:16:47Z
2007-03-27T04:16:47Z
2001-05
 
Type Electronic Thesis and Dissertation
 
Format 2066890 bytes
application/pdf
 
Identifier http://etd.iisc.ernet.in/handle/2005/268
null
 
Language en
 
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