New carbon-carbon bond forming reactions of cyclic sulfate esters and cyclic sulfamidates

Article abstract of DOI:10.1016/S0040-4039(02)00138-7

Carbon-carbon bonding forming reactions of two cyclic sulfate esters and a cyclic sulfamidate are reported, the former with lithium dianions to give substituted tetrahydrofuran derivatives with displacement of sulfate, and the latter undergoes ring-openin

Full text of DOI:10.1016/S0040-4039(02)00138-7

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 43 (2002) 1915–1918
New carbonꢀcarbon bond forming reactions of cyclic sulfate
esters and cyclic sulfamidates
Melanie K. Pound, Darren L. Davies, Melanie Pilkington, Maria M. de Pina Vaz Sousa
and John D. Wallis*
Department of Chemistry and Physics, The Nottingham Trent University, Clifton Lane, Nottingham NG11 8NS, UK
Received 5 December 2001; accepted 18 January 2002
Abstract—Carbon–carbon bonding forming reactions of two cyclic sulfate esters and a cyclic sulfamidate are reported, the former
with lithium dianions to give substituted tetrahydrofuran derivatives with displacement of sulfate, and the latter undergoes
ring-opening monosubstitution reactions with stabilised organolithiums and an organocuprate species. © 2002 Elsevier Science
Ltd. All rights reserved.
3
Cyclic sulfate esters of vic-diols and cyclic sulfamidates
of vic-aminoalcohols are of interest as synthetic inter-
mediates since their precursors are available as single
enantiomers from alkenes by asymmetric methodolo-
reported, for example with cyanide, a Grignard
3
12
reagent with copper catalysis, and lithiated alkynes
13
and 1,3-dithiane derivatives. The disubstitution reac-
tion with malonate and related species has found con-
siderable application in the preparation of cyclo-
1
,2
gies introduced by Sharpless.
Cyclic sulfate esters
3,14
undergo single substitution reactions at a ring carbon
with a range of nitrogen, oxygen and sulfur based
nucleophilic species to give the substituted alcohol after
propane derivatives.
We now report double substitution reactions of the
racemic cyclic sulfate esters 1 and 2 with a range of
dianions generated from molecules of general formula
CH COCHR-X, where X is CH C(O)-, CH O C- and
3
,4
hydrolysis of the resulting hemi-sulfate. They have
found applications in the syntheses of natural prod-
5
6
ucts, biologically active materials and heterocyclic
3
3
3
2
7
8
15
systems and also in cascade reactions. Several double
substitution reactions with bis-nucleophiles leading to
the loss of sulfate have also been reported, notably with
dithiolates to give fused dihydro(1,4)dithiins of use in
the synthesis of chiral organosulfur donors, with
sulfide to give episulfides and with amidines to give
PhSO -, by treatment with LDA.
For example,
2
16
reaction of the lithium dianion of pentane-2,4-dione 3
with cyclic sulfate ester 1 in THF gave after chromatog-
raphy both the E- and Z-stereoisomers of the 5-substi-
tuted tetrahydrofuran-2-ylideneacetate 6 and 12 in 42
and 30% yields (Table 1). Attack of the terminal carbon
of the dianion at the primary carbon of 1 is followed by
attack of oxygen at the secondary centre, this latter
9
1
0
1
1
diamines. Several monosubstitution reactions with a
variety of carbon centred nucleophiles have been
Table 1. Yields of products from reaction of dianions with cyclic sulfate esters
Source of dianion
Cyclic sulfate ester
Product yield (%),17 E-isomer
Product, yield (%), Z-isomer
3
4
5
1
2
1
2
1
2
1
1
6 (42)
8 (40)
7 (43)
9 (41)
–
10 (23)
18 (45)
19 (66)
12 (30)
15 (16)
13 (7)
–
14 (25)
–
–
–
1
1
6
7
Keywords: cyclic sulfate esters; tetrahydrofurans; cyclic sulfamidates.
*
Corresponding author.
0
040-4039/02/$ - see front matter © 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(02)00138-7

1
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M. K. Pound et al. / Tetrahedron Letters 43 (2002) 1915–1918
reaction preferring displacement of sulfate by the
harder’ oxygen centre of the enolate. The two com-
pounds were distinguished by their chemical shifts and
NOE difference spectra, indicating a NOE effect
monosubstituted at the methylene position, also reacted
in the same way with cyclic sulfate ester 1 to give
tetrahydrofurans 18 and 19, a reaction which could find
application in the synthesis of derivatives of methyl
nonactate 20 and thus nonactins.
‘
between the vinyl H atom and the 3-CH group in 12
2
but not in 6, and comparison with compounds in the
literature. The minor isomer 12 slowly isomerised to the
major isomer at room temperature, but this is sup-
pressed below 0°C.
The synthesis of such tetrahydrofuranylidenes has also
19
been effected by reaction of epoxides with dianions or
20
bis(trimethylsilyloxy)-1,3-butadienes.
In both these
approaches the reactions proceed via inversion of
configuration at one site only on the epoxide ring (the
position of C,C bond formation at the less hindered
site) so cannot be used to give enantiopure 4,5-trans
disubstituted products. Reactions of epibromohydrins
with dianions also yield alkylidenetetrahydrofuran
Reaction of the b-ketoester 4 with cyclic sulfate ester 1
under similar conditions gave the corresponding tetra-
hydrofuran derivative as E- and Z-isomers 7 and 13 in
4
3 and 7% yields, respectively, with 13 isomerising to 7
slowly. However, the dianion from b-ketosulfone 5
reacted with 1 to give only the Z-isomer of the tetra-
hydrofuran derivative 14, identified by comparison of
21
derivatives. Tetrahydrofuran 6 has been prepared
1
from the corresponding tetrahydrofuran-2-thione and
H chemical shifts with the corresponding 5-unsubsti-
22
23
1
8
methyl bromozincacetate. Hoye and Crawford have
reported ring opening of the cyclic sulfate ester of
dodecane-1,2-diol by several simple lithium enolates.
They found that the lithium enolate of t-butyl acetate
gave tetrahydrofuran 11 as a by-product, probably
because under the conditions the starting material
underwent Claisen condensation to a b-ketoester. A
related synthesis of (S)-coniine via double substitution
on a cyclic sulfate ester of a 1,3-diol with the disodium
salt of N-tosyl tosylacetamide has been reported
tuted analogues.
Reactions of the dianions with the disubstituted cyclic
sulfate ester 2 were also successful, even though both
nucleophilic displacements are at secondary carbon
atoms. Dianions of compounds 3–5 gave useful yields
of the 2,4,5-trisubstituted tetrahydrofuran derivatives
8–10, all of which have E stereochemistry at the alkenyl
bond. The b-diketone 3 also gave some of the alterna-
tive stereoisomer 15. It was of particular interest to find
that the b-ketoester 16 and b-diketone 17, which are
24
recently.

M. K. Pound et al. / Tetrahedron Letters 43 (2002) 1915–1918
1917
The chemistry of cyclic sulfamidates has not received as
much attention as that of cyclic sulfate esters, however,
nucleophilic ring opening of cyclic sulfamidates of vic-
aminoalcohols by attack at the 5-C atom followed by
acidic hydrolysis of the sulfamate salt have been investi-
treated with lithium di(n-butyl)cuprate at −20°C, and
subsequently hydrolysed with 20% sulfuric acid to give
the amine 28 in 23% yield. The cyclic sulfamidate of
N-benzylthreonine methyl ester yielded a 3:1 mixture of
diastereoisomers in 40% yield from the corresponding
reaction. Further carbon, carbon bond forming reac-
tions of cyclic sulfate esters and sulfamidates are under
investigation.
2
5–28
gated in a number of groups.
We report here
several substitution reactions by carbon centred nucle-
ophilic species. The cyclic sulfamidate 22 was prepared
in two steps from N-benzylalaninol by treatment with
thionyl chloride and pyridine in THF to give the cyclic
sulfamidite 21 as a mixture of two diastereoisomers and
subsequent oxidation with sodium periodate and cata-
lytic ruthenium trichloride in 37% overall yield.
Acknowledgements
We thank the EPSRC Mass Spectrometry Service for
data, The Nottingham Trent University for a stu-
dentship, and the Chemistry Department, University of
Warwick for the measurements of nuclear Overhauser
effects.
Lithiated acetonitrile was treated with cyclic sulfami-
date 22 at −78°C and left to warm to room temperature
overnight to give the lithium sulfamate 24 in 90% yield.
Hydrolysis of this product with aqueous sulfuric acid
(
pH 2) gave 4-benzylaminopentanenitrile 25 in 73%
yield. Reaction of the cyclic sulfamidite 21 or the
2
5
bicyclic sulfamidate of prolinol, 23, with lithiated
acetonitrile under similar conditions led to a mixture of
products. Lithiated 1,3-dithiane was reacted with cyclic
sulfamidate 22 at −25°C and left to warm to room
temperature for 24 h to give the lithium sulfamate 26 in
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