Diastereoselective reactions and rearrangements of chiral allylic sulfoximines

Article abstract of DOI:10.1080/10426509708545524

The nucleophilic and electrophilic chemistry of chiral allylic sulfominines and their alkyl sulfoximine counterparts are described including the synthesis of highly functionalised cyclopropanes derivatives. The synthesis of primary and secondary N-tosyl a

Full text of DOI:10.1080/10426509708545524

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Phosphorus, Sulfur, and Silicon
and the Related Elements
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Diastereoselective Reactions and
Rearrangements of Chiral Allylic
Sulfoximines
Stephen G. Pyne , Z. Dong , D. M. David & G. W. O'Meara
a
Department of Chemistry , University of Wollongong ,
Wollongong, NSW 2522, Australia
b
Department of Chemistry , University of Wollongong ,
Wollongong, NSW 2522, Australia
c
Department of Chemistry , University of Wollongong ,
Wollongong, NSW 2522, Australia
d
Department of Chemistry , University of Wollongong ,
Wollongong, NSW 2522, Australia
Published online: 17 Mar 2008.
To cite this article: Stephen G. Pyne , Z. Dong , D. M. David & G. W. O'Meara (1997)
Diastereoselective Reactions and Rearrangements of Chiral Allylic Sulfoximines,
Phosphorus, Sulfur, and Silicon and the Related Elements, 120:1, 275-289, DOI:
10.1080/10426509708545524
To link to this article: http://dx.doi.org/10.1080/10426509708545524
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DIASTEREOSELECTIVE REACTIONS OF CHIRAL ALLYLIC SULFOXIMINES
283
the relative rates of the reactions of (12d), (12e) and (12f) correlated closely with the
electron withdrawing ability of the N-substituent of the sulfoximine. Thus while (12d)
reacted in 10 rain, (12e) required a reaction time of 30 rain while the reaction of JV-rnethyl
compound (12f) was complete only after 1 h. In the later reaction the major product isolated
was iV-methyl phenylsulfinamide (68 %).
Scheme
1
1
R ,
R
Pd(0)
Pd(0)
PhSONTS
.
^
S — P h
XNTs
NTs
8)
(
12)
(
2
N(Ts)R
(
9); R = SOPh
OH"
2
(
10);R = H
(
iii) Chiral a-substituted
Allylic
Sulfoximines
In principle the palladium(O) catalysed rearrangement reaction of optically active oc.y-
disubstituted allylic sulfoximines can give rise to optically active allylic amines. The success
of this reaction depends upon the regioselectivity and diastereoselectivity of the rearrangement
reaction. Methylation of the (S)-allylic sulfoximines (12c), (12d) and (12e) (ee = 96%) by
first deprotonation with LDA at -78°C and then methylation with Mel gave the corresponding
methylated allylic sulfoximines (13a), (13b) and (13c) respectively in 96-98% de (Scheme
6
). These cc-methylated sulfoximines were unstable and their attempted purification by
chromatography gave complex mixtures that included rearranged allylic sulfinamides.
Scheme 6.
(
(
(
12c;R = Ts,n= 1)
12d;R = Ts,n = 2)
12e;R = C0 Me,n = 2)
(13b;R = Ts,n = 2)
(13c;R = C0 Me,n = 2)
2
2