Synthesis of (-)-Geissman Waiss Lactone, cis gamma-butyrolactone derivatives and gamma-peptides (original) (raw)
Related papers
Recent Developments in γ-Lactone Synthesis
Mini-reviews in Organic Chemistry, 2009
In recent years, several classes of biologically active molecules containing the -lactone ring, pesticides, plant and fungal growth inhibitors, and antibiotics have been found. Thus the synthesis of substituted dihydrofuran-2(3H) ones is a continuously developing area. Few general synthetic approaches to their stereoselective synthesis with broad structural variety are known. This article reviews the latest developments in the synthesis of -butyrolactones. We focus on the ring-closing steps and pay special attention to how different authors obtain the correspondent 4-hydroxycarbonyl compound; an acyclic synthon for the -lactone ring.
Recent Developments in ?-Lactone Synthesis
Mini Rev Org Chem, 2009
In recent years, several classes of biologically active molecules containing the -lactone ring, pesticides, plant and fungal growth inhibitors, and antibiotics have been found. Thus the synthesis of substituted dihydrofuran-2(3H) ones is a continuously developing area. Few general synthetic approaches to their stereoselective synthesis with broad structural variety are known. This article reviews the latest developments in the synthesis of -butyrolactones. We focus on the ring-closing steps and pay special attention to how different authors obtain the correspondent 4-hydroxycarbonyl compound; an acyclic synthon for the -lactone ring.
European Journal of Medicinal Chemistry, 2006
The synthesis of a series of α-methylene-γ-butyrolactones (compounds 4a, 4b, 6-12, 16, 17) and α,β-unsaturated-δ-lactones (compounds 19 −23, 25, 26) starting from 4,4-dimethyldihydrofuran-2,3-dione (1) has been described. Their chemical structures were assigned by spectroscopic evidence. These new compounds exhibited significantly different antiproliferative properties against cultured human tumor cell lines with their IC 50 values ranging from 0.88 to > 20.00 μM.
Recent Developments in γ-Lactone Synthesis
Mini-Reviews in Organic Chemistry, 2009
In recent years, several classes of biologically active molecules containing the -lactone ring, pesticides, plant and fungal growth inhibitors, and antibiotics have been found. Thus the synthesis of substituted dihydrofuran-2(3H) ones is a continuously developing area. Few general synthetic approaches to their stereoselective synthesis with broad structural variety are known. This article reviews the latest developments in the synthesis of -butyrolactones. We focus on the ring-closing steps and pay special attention to how different authors obtain the correspondent 4-hydroxycarbonyl compound; an acyclic synthon for the -lactone ring.
2023
The asymmetric synthesis of methyl or pentyloxy N,O-bicyclic γ-butyrolactone lactams, 6-aminocyclohex-3-ene-1,2-diol (an oseltamivir precursor) and β-hydroxy lactam tripeptide, starting from (-)-(1S,2S)-1azido-2-hydroxycyclohexene is hereby described. Synthetic transformations in the developed protocols include a linear relay of reduction/protection of the azide, allylic hydroxylation, alcoholysis, oxidative cleavage promoting lactonization/lactamization sequences and methylation. This route provides a simple synthetic pathway towards necine alkaloid derivatives, the antiviral drug oseltamivir (Tamiflu) and peptides incorporating rigid lactam units for foldamer synthesis thus extending the usefulness of our previously reported asymmetric synthetic methodology.
Tetrahedron Letters, 1990
4-Cyclohexyl 3,3_disubstituted oxetan-2-ones rearrange under Lewis acid catalysis to afford trans.-fused cycloheptano butyrolactones. A host of natural products, most notably the guaianolide and pseudoguaiaqolides, contain a butyrolactone which is trans-fused to a cycloheptane ring, and2a number of ingenious techniques have been reported for their synthesis. The primary difficulties in guaianolide synthesis reside in the construction of the seven-membered ring, complete with stereochemically defined substi-tuents, and fixation of the trans lactone ring in a highly stereoselective manner. An attractive approach to the synthesis of these molecules would involve the functionalization of a cyclohexane ring, where stereochemical control is considerably more facile, followed by expansion to the cycloheptyl homolog with simultaneous formation of the required translactone. Mars?all's elegant cyclopropylcarbinol solvolysis scheme exemplifies this strategy. We now wish to report a short, conceptually unique synthetic method which accomplishes the construction of cycloheptano trans-fused butyrolactones in three steps from six-membered carbocyclic precursors. We have recently reported a number of useful lactzne syntheses based on the rearrangement of alkyl-or cycloalkyl B-la&ones. As illustrated below, cyclohexyl A-lactones 2 (derived in two steps from the aldehyde 1) are transformed into Spiro butyrolactones 3 when the ring is situated trans to a 3-substituent, since rotation of the cyclohexyl-la&one bond is relatively a=RCHtiCO& b=PhSO&I; c=MgBr, 6617 administered by the American Chemical Society, in addition to the Research Corporation, for support of this work. The 300 MHz NMR instrument was acquired with the help of the National Science Foundation (CHE-8815619). 1. 25.0, 24.9, 22.8, 22.7 ppm; TLC (CH2C12) Rf 0.41. Canonne, P.; Belanger, D.; Lemay, G.; Foscolos, G.B. J. Org. Chem. 1981, 46, 3091.
The Journal of Organic Chemistry, 1990
Concise syntheses of carboxylic ester and n-propyl-substituted 7-lactam-constrained derivatives 7a,b and 18a,b, starting from commercially available N-t-Boc-L-Asp(0Bz)OH (4), are described. Esterification of 4, followed by regioselective formylation, gave the key intermediate 6 (79%, two steps), which served as a common precursor in both lactam series. Reductive amination of 6 with phenylalanine amide, followed by in situ cyclization of the resulting amino ester, provided the 7-lactam-constrained dipeptide products 7a (24%) and 7b (41%). Alkylation of 6 with allyl iodide furnished a mixture of 0and C-allylated products 14 and 15 in 77% and 10% yields, respectively. Thermal Claisen rearrangement of 14 afforded additional 15 (66%), which was then converted to the aldehyde 16 (75%). Reductive amination of 16 with amino acid diester derivative 17 and subsequent lactam closure produced the dipeptide isosteres 18a (31%) and 18b (29%). The relative stereochemistry of the lactam ring substituents was determined by 'H NMR using spinspin decoupling and NOE enhancement experiments. Proof that less than 5% racemization occurred during the preparation of 6 was provided by the independent conversion of 5 to the diastereomeric MTPA esters 11 and 12 and comparison of the 'H NMR spectra of these two compounds to the MTPA ester product mixture of 11 and the enantiomer of 12 derived from 6. Verification that no additional epimerization of the a-carbon in 6 occurred during any of the subsequent processes leading to 7 or 18 was furnished by HPLC analysis of the crude product mixture resulting from the reductive amination and cyclization of 6 and 16 with the D-enantiomers of phenylalanine amide and 17, respectively. (8) (a) Danishefsky, S.; Berman, E.; Clizbe, L. A.; Hirama, M. J. Am. Chem. SOC. 1979,101, 4385. (b) Danishefsky, S.; Morris, J.; Clizbe, L. A.