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Volumn 56, Issue 4, 2000, Pages 677-683

Aldol reactions with erythrulose derivatives: Stereoselective synthesis of differentially protected syn-α,β-dihydroxy esters

Author keywords

Aldol reactions; Diastereoselection; Hydroxy acids and derivatives; Oxidation

Indexed keywords

ALDEHYDE DERIVATIVE; CARBOHYDRATE DERIVATIVE; ERYTHRULOSE DERIVATIVE; GLYCOLIC ACID DERIVATIVE; UNCLASSIFIED DRUG;

EID: 0034695654     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(99)01041-8     Document Type: Article
Times cited : (31)

References (74)
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    • For the preparation of variously protected D- and L-erythrulose derivatives using chiral precursors other than erythrulose itself, see
    • For the preparation of variously protected D- and L-erythrulose derivatives using chiral precursors other than erythrulose itself, see: Marco, J. A.; Carda, M.; González, F.; Rodríguez, S.; Murga, J. Liebigs Ann. Chem. 1996, 1801-1810. For an improved preparation of silylated L-erythrulose acetonides 6 (R=TES, TBS, TPS) from L-erythrulose hydrate, see: Carda, M.; Rodríguez, S.; Murga, J.; Falomir, E.; Marco, J. A.; Röper, H. Synth. Commun. 1999, 29, 2601-2610.
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    • For an improved preparation of silylated L-erythrulose acetonides 6 (R=TES, TBS, TPS) from L-erythrulose hydrate, see
    • For the preparation of variously protected D- and L-erythrulose derivatives using chiral precursors other than erythrulose itself, see: Marco, J. A.; Carda, M.; González, F.; Rodríguez, S.; Murga, J. Liebigs Ann. Chem. 1996, 1801-1810. For an improved preparation of silylated L-erythrulose acetonides 6 (R=TES, TBS, TPS) from L-erythrulose hydrate, see: Carda, M.; Rodríguez, S.; Murga, J.; Falomir, E.; Marco, J. A.; Röper, H. Synth. Commun. 1999, 29, 2601-2610.
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    • Brown, H. C.; Ganesan, K.; Dhar, R. K. J. Org. Chem. 58, 147-153. For a general review on boron aldol additions, see: Cowden, C. J.; Paterson, I. Org. React. 1997, 51, 1-200.
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    • For a general review on boron aldol additions, see
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    • A preliminary account of the part of the work described here has already appeared
    • A preliminary account of the part of the work described here has already appeared: Marco, J. A.; Carda, M.; Falomir, E.; Palomo, C.; Oiarbide, M.; Ortiz, J. A.; Linden, A. Tetrahedron Lett. 1999, 1065-1068. For the influence of the protecting groups on the stereoselectivity, see: Carda, M.; Falomir, E.; Murga, J.; Castillo, E.; González, F.; Marco, J. A. Tetrahedron Lett. 1999, 6845-6848.
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    • For the influence of the protecting groups on the stereoselectivity, see
    • A preliminary account of the part of the work described here has already appeared: Marco, J. A.; Carda, M.; Falomir, E.; Palomo, C.; Oiarbide, M.; Ortiz, J. A.; Linden, A. Tetrahedron Lett. 1999, 1065-1068. For the influence of the protecting groups on the stereoselectivity, see: Carda, M.; Falomir, E.; Murga, J.; Castillo, E.; González, F.; Marco, J. A. Tetrahedron Lett. 1999, 6845-6848.
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    • The complete details of all reaction conditions, chemical correlations, X-ray diffraction analysis, computational calculations and physical and spectral data of all intermediates are described in the PhD Thesis of E. Falomir (University of Castellón, 1998)
    • The complete details of all reaction conditions, chemical correlations, X-ray diffraction analysis, computational calculations and physical and spectral data of all intermediates are described in the PhD Thesis of E. Falomir (University of Castellón, 1998).
  • 49
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    • Even though any one of the three silyl groups (TES, TBS and TBDPS) is suitable as a protecting group under the reaction conditions of the sequence 7→8→9→10; here we describe only those esters 8 and 9 bearing a TBS group
    • Even though any one of the three silyl groups (TES, TBS and TBDPS) is suitable as a protecting group under the reaction conditions of the sequence 7→8→9→10; here we describe only those esters 8 and 9 bearing a TBS group.
  • 52
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    • The formation of small amounts of the deformylated ester 9 during the oxidative cleavage of 8 could not be avoided: shorter reaction times only led to incomplete oxidation of 7. However, the mixture of 8 and 9 may be used without separation in either of the subsequent reactions, thus improving the overall yields
    • The formation of small amounts of the deformylated ester 9 during the oxidative cleavage of 8 could not be avoided: shorter reaction times only led to incomplete oxidation of 7. However, the mixture of 8 and 9 may be used without separation in either of the subsequent reactions, thus improving the overall yields.
  • 53
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    • The formylated derivatives 8 are quite sensitive to alkaline media. Hydrolysis of 8 under even such mild conditions as potassium carbonate in MeOH at 0°C caused decomposition. The same result was observed when 8 (or 9) was treated with tetra-n-butylammonium fluoride in THF
    • The formylated derivatives 8 are quite sensitive to alkaline media. Hydrolysis of 8 under even such mild conditions as potassium carbonate in MeOH at 0°C caused decomposition. The same result was observed when 8 (or 9) was treated with tetra-n-butylammonium fluoride in THF.
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    • Dihydroxy ester 10 (R′=Ph) showed NMR data identical with those reported
    • Dihydroxy ester 10 (R′=Ph) showed NMR data identical with those reported: Wang, Z.-M.; Kolb, H. C.; Sharpless, K. B. J. Org. Chem. 1994, 59, 5104-5105.
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    • Wang, Z.-M.1    Kolb, H.C.2    Sharpless, K.B.3
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    • For recent theoretical studies on boron aldol reactions, see: (a)
    • For recent theoretical studies on boron aldol reactions, see: (a) Li, Y.; Paddon-Row, M. N.; Houk, K. N. J. Org. Chem. 1990, 55, 481-493.
    • (1990) J. Org. Chem. , vol.55 , pp. 481-493
    • Li, Y.1    Paddon-Row, M.N.2    Houk, K.N.3
  • 72
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    • Computational ab initio calculations have been performed by Dr J. Murga. The results will be disclosed in due time
    • Computational ab initio calculations have been performed by Dr J. Murga. The results will be disclosed in due time.
  • 73
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    • 19 it has been suggested that initial formation of a five-membered chelate involving the boron and the two oxygen atoms, followed by stereoselective deprotonation by the tertiary amine, explain the formation of the putative Z enolate. This and other alternative explanations are now being studied by us at both the theoretical and the experimental level
    • 19 it has been suggested that initial formation of a five-membered chelate involving the boron and the two oxygen atoms, followed by stereoselective deprotonation by the tertiary amine, explain the formation of the putative Z enolate. This and other alternative explanations are now being studied by us at both the theoretical and the experimental level.


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