134453-13-7Relevant academic research and scientific papers
Asymmetric synthesis of (-)-tetrahydrolipstatin from a β-hydroxy- δ-oxo sulfoxide
Raghavan, Sadagopan,Rathore, Kailash
scheme or table, p. 1285 - 1288 (2009/12/01)
An asymmetric synthesis of (-)-tetrahydrolipstatin is described. A palladium-catalyzed regioselective oxidation of an alkene to a ketone, highly diastereoselective reduction of a β-hydroxy ketone, selective oxidation of a diol, and modular synthesis are the key features of the synthesis. Georg Thieme Verlag Stuttgart.
Asymmetric synthesis of (-)-tetrahydrolipstatin
Raghavan, Sadagopan,Rathore, Kailash
experimental part, p. 10083 - 10092 (2010/02/27)
Attempts toward the asymmetric synthesis of (-)-tetrahydrolipstatin are described. A palladium catalyzed Wacker-type reaction to convert an alkene to a ketone, highly diastereoselective reduction of a β-hydroxy ketone, selective oxidation of a diol, and modular synthesis are the key features of the successful approach.
Stereocontrol in organic synthesis using silicon-containing compounds. A synthesis of (-)-tetrahydrolipstatin using the alkylation of a β-silyl ester and the hydroboration of an allylsilane
Fleming, Ian,Lawrence, Nicholas J.
, p. 2679 - 2686 (2007/10/03)
Conjugate addition of bis(Z-tridec-1-enyl)cuprate Z-10 to (5S)-1-[(Z)-3′-dimethyl(phenyl)silylprop-2-enoyl]-5-(trityloxymethyl) pyrrolidin-2-one Z-6 gave the 3A-imide Z-12. Subsequent enolate n-hexylation of the benzyl ester Z-13a derived from this imide gave the 2R,3S-ester Z-14a. Reduction of the ester group and protection of the alcohol as its TBDMS group gave the allylsilane (Z)(7 R,8S)-7-(tert-butyldimethylsilyloxymethyl)-8-dimethyl(phenyl)silylhenicos-9-ene Z-15. Hydroboration-oxidation gave the 7R,8S,10S-alcohol 16. Protection of the C-10 hydroxy as its benzyl ether, removal of the silyl protecting group and oxidation gave (2R,3S,5S)-5-benzyloxy-3-dimethyl(phenyl)silyl-2-hexylhexadecanoic acid 19. Silyl-to-hydroxy conversion, β-lactone formation, and hydrogenolysis gave the known alcohol (3S,4S)-3-hexyl-4-[(S)-2′-hydroxytridecyl]oxetan-2-one 22, from which tetrahydrolipstatin 1 was prepared by a conventional esterification. Each of the stereochemistry determining steps, 4 → Z-6, 7 → E-8, E-8 → Z-9, Z-6 + Z-10 → Z-12, Z-13a → Z-14a and Z-15 → 16, took place with a remarkably high level of open-chain stereocontrol.
Synthesis of Tetrahydrolipstatin
Chadha, N. K.,Batcho, A. D.,Tang, P. C.,Courtney, L. F.,Cook, C. M.,et al.
, p. 4714 - 4718 (2007/10/02)
An asymmetric synthesis of tetrahydrolipstati (4) is described.Application of our previously described in situ cyclopentadiene alkylation-asymmetric hydroboration protocol provided the key chiral alcohol 9.In the course of this work, the presence of a free hydroxyl group was found to exert a strong directing effect on the regioselectivity of a Baeyer-Villiger reaction (16 --> 17).Subsequent transformations of lactone 17 produced tetrahydrolipstatin.
A synthesis of (-)-tetrahydrolipstatin in which the relative stereochemistry is controlled by a phenyldimethylsilyl group
Fleming, Ian,Lawrence, Nicholas J.
, p. 3645 - 3648 (2007/10/02)
The alkylation ofa β-silylenolate and the hydroboration of an allylsilane successively control the relative stereochemistry of the three stereogenic centres on the carbon backbone in a synthesis of the esterase inhibitor tetrahydrolipstatin (21).
