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and Claisen-type dimerization of five aldonolactones have been
DOI: 10.1039/C9CC09093B
Table 3. Claisen-type dimerization of aldonolactone derivatives 7-11
realized. These transformations provide a novel type of
branched higher carbon sugars effectively, wherein the regio-
and stereo-selectivities can be well controlled by the
substituents on the starting aldosuloses/aldonolactones. It is
noteworthy that the isopropylidene group installed at the α,β-
position of the carbonyl group in the monosaccharide
substrates plays an indispensable role in these reactions.
Otherwise, α-epimerization and β-elimination of the carbonyl
compounds having hetero-atoms at the α/β positions can occur
easily under basic conditions. Further transformations of the
resultant higher carbon sugars into biologically active
compounds are a current project of us and the results will be
reported in due course.
O
O
RO
O
NaHMDS (0.7 equiv), THF, -78 °C;
then TMSCl (0.7 equiv)
O
O
RO
OR
TMSO
7a 11a
7 11
-
-
Entry
Aldonolactone
Dimer (Isolated yield)
O
O
O
O
O
O
O
O
O
O
O
O
O
O
1
2
O
TMSO
O
O
7
O
O
7a
(86%)
Financial support from the National Natural Science
Foundation of China (21861162011, 21432012, and 21621002)
and K. C. Wong Education Foundation is gratefully
acknowledged.
O
O
O
O
O
O
O
O
O
O
O
O
TMSO
O
O
8
O
O
Notes and references
8a
(78%)
1
S. Wang, J. Sun, Q. Zhang, X. Cao, Y. Zhao, G. Tang and B. Yu,
Angew. Chem. Int. Ed., 2018, 57, 2884-2888.
S. Wang, Q. Zhang, Y. Zhao, J. Sun, W. Kang, F. Wang, H. Pan,
G. Tang and B. Yu, Angew. Chem. Int. Ed., 2019, 58, 10558-
10562.
2
TIPSO
O
O
O
O
TIPSO
O
O
3
4
5
D. Horton and E. K. Just, Carbohydr. Res., 1969, 9, 129-137.
D. Horton and E. K. Just, Carbohydr. Res., 1971, 18, 81-94.
J. M. J. Tronchet and M. J. Tronchet, Helv. Chim. Acta, 1970,
53, 1174-1180.
O
3
4
5
O
OTIPS
TMSO
9
O
O
9a
(94%)
6
7
P. M. Collins and R. Iyer, Carbohydr. Res., 1976, 46, 277-283.
P. Köll, J. Schulz and K. Heyns, Chem. Ber., 1979, 112, 2337-
2341.
O
O
O
O
O
8
9
R. Csuk, M. Schaade and A. Schmidt, Tetrahedron, 1994, 50,
11885–11892.
R. Csuk, U. Höring and M. Schaade, Tetrahedron, 1996, 52,
9759-9776.
O
O
O
O
O
O
O
O
10
O
O
OTMS
10 K. Kuramochi, H. Itaya, S. Nagata, T. Ken-ichi and S.
Kobayashi, Tetrahedron Lett., 1999, 40, 7367-7370.
11 K. Kuramochi, S. Nagata, H. Itaya, Y. Matsubara, T. Sunoki, H.
Uchiro, K. Takao and S. Kobayashi, Tetrahedron, 2003, 59,
9743-9758.
12 S. Jarosz, J. Carbohydr. Chem., 2001, 20, 93-107.
13 S. Jarosz, Curr. Org. Chem., 2008, 12, 985-994.
14 A. Osuch-Kwiatkowska, M. Cieplak and S. Jarosz, Curr. Org.
Chem., 2014, 18, 327-340.
O
O
10a
(69%)
O
O
O
O
O
O
O
O
O
OTMS
11
O
O
11a
(74%)
exist as mixtures of anomers and open-chain hydroxyl ketones,
therefore were immediately protected by silylation for the
convenience of isolation and characterization. These two-step
transformations provided the corresponding dimeric 1’-O-
trimethylsilyl (TMS) derivatives 7a-11a in satisfactory yields (69%-
94%). The structures of dimers 7a and 11a8 were confirmed
unambiguously by X-ray diffraction analysis (CCDC 1892035 and
1892034). It is noteworthy that dimers 8a and 10a, which were
prepared from L/D-gulose lactones, respectively, can be
regarded as the homo-coupling products of D/L-glucose.
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