One-pot synthesis of enantiopure syn-1,3-diacetates from racemic syn/anti mixtures of 1,3-diols by dynamic kinetic asymmetric transformation

Edin, M.; Steinreiber, J.; Bäckvall, J-E.

Proceedings of the National Academy of Sciences of the United States of America 101(16): 5761-5766

ISSN/ISBN: 0027-8424

2004

PMID: 15069194

DOI: 10.1073/pnas.0307146101

Document: 007814525

A one-pot synthesis of enantiomerically pure syn-1,3-diacetates starting from readily accessible racemic diastereomeric mixtures of 1,3-diols has been realized by combining (i) enzymatic transesterification, (ii) ruthenium-catalyzed epimerization of a secondary alcohol in a diol or diol monoacetate, and (iii) intramolecular acyl migration in a syn-1,3-diol monoacetate. The in situ coupling of these three processes results in an efficient enantioselective synthesis of acyclic syn-1,3-diacetates via combined deracemization-deepimerization and constitutes a dynamic kinetic asymmetric transformation concept. Several differently substituted unsymmetrical, acyclic syn-1,3-diacetates were obtained in yields up to 73% with excellent enantioselectivities (>99%) and good diastereomeric ratios (>90% syn).

Related Documents

Highly efficient synthesis of enantiopure diacetylated C(2)-symmetric diols by ruthenium- and enzyme-catalyzed dynamic kinetic asymmetric transformation (DYKAT). Chemistry 12(23): 6053-6061

Enantiopure 1,5-diols from dynamic kinetic asymmetric transformation. Useful synthetic intermediates for the preparation of chiral heterocycles. Organic Letters 10(10): 2027-2030

Enzyme- and ruthenium-catalyzed dynamic kinetic asymmetric transformation of 1,5-diols. Application to the synthesis of (+)-Solenopsin A. Journal of Organic Chemistry 74(5): 1988-1993

Ruthenium- and enzyme-catalyzed dynamic kinetic asymmetric transformation of 1,4-diols: synthesis of gamma-hydroxy ketones. Journal of Organic Chemistry 69(26): 9191-9195

Copper-Catalyzed Asymmetric Allylic Alkylation of Racemic Cyclic Substrates: Application of Dynamic Kinetic Asymmetric Transformation (DYKAT). Advanced Synthesis and Catalysis 352(2-3): 447-457

Dynamic kinetic asymmetric transformation of 1,4-diols and the preparation of trans-2,5-disubstituted pyrrolidines. Tetrahedron Letters 50(26): 3237-3240

Non-enzymatic dynamic kinetic resolution of racemic α-arylalkanoic acids: an advanced asymmetric synthesis of chiral nonsteroidal anti-inflammatory drugs (NSAIDs). Catalysis Science and Technology 2(11): 2200

Tandem-Bisalkylation of 2-Trialkylsilyl-1,3-dithiane: A New Sequential Transformation for the Synthesis of C 2 -Symmetrical Enantiopure 1,5-Diols and ,-Dihydroxyketones as well as of Enantiopure 1,3,5-Triols. Synlett 1994(7): 511-512

Lewis Acid Catalyzed Dynamic Kinetic Asymmetric Transformation of Racemic N-Sulfonylaziridines. Journal of the American Chemical Society 140(49): 17211-17217

Enantioselective synthesis of syn- and anti-1,3-aminoalcohols via β-aminoketones and subsequent reduction/dynamic kinetic asymmetric transformation. Journal of the American Chemical Society 132(43): 15182-15184