FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2117582597> ?p ?o ?g. }

• W2117582597 endingPage "3608" @default.
• W2117582597 startingPage "3596" @default.
• W2117582597 abstract "A concise total synthesis of spirastrellolide A methyl ester (1 a, R(1) =Me) as the parent compound of a series of highly cytotoxic marine macrolides is disclosed, which exploits and expands the flexibility of a synthesis plan previously developed by our group en route to the sister compound spirastrellolide F methyl ester (6 a, R(1) =Me). Key to success was the masking of the signature Δ(15,16) -bond of 1 a as a C16-carbonyl group until after the stereogenic center at C24 had been properly set by a highly selective hydrogenation of the C24 exo-methylene precursor 66. Conformational control over the macrocyclic frame allowed the proper stereochemical course to be dialed into this reduction process. The elaboration of the C16 ketone to the C15-C16 double bond was accomplished by a chemoselective alkenyl triflate formation followed by a palladium-catalyzed hydride delivery. The role of the ketone at C16 as a strategic design element is also evident up-stream of the key intermediate 66, the assembly of which hinged upon the addition of the polyfunctionalized dithiane 37 to the similarly elaborate aldehyde fragment 46. Other crucial steps of the total synthesis were an alkyl-Suzuki coupling and a Yamaguchi lactonization that allowed the Northern and the Southern sector of the target to be stitched together and the macrocyclic perimeter to be forged. The lateral chain comprising the remote C46 stereocenter was finally attached to the core region by a modified Julia-Kocienski olefination. The preparation of the individual building blocks led to some methodological spin-offs, amongst which the improved procedure for the N-O-bond cleavage of isoxazolines by zero-valent molybdenum and the ozonolysis of a double bond in the presence of other oxidation-prone functionality are most noteworthy. Preliminary biological data suggest that the entire carbon framework, that is the macrocyclic core plus the lateral chain, might be necessary for high cytotoxicity." @default.
• W2117582597 created "2016-06-24" @default.
• W2117582597 creator A5054667122 @default.
• W2117582597 creator A5060462612 @default.
• W2117582597 creator A5060729497 @default.
• W2117582597 creator A5062152837 @default.
• W2117582597 creator A5068723001 @default.
• W2117582597 date "2013-02-18" @default.
• W2117582597 modified "2023-10-16" @default.
• W2117582597 title "A Total Synthesis of Spirastrellolide A Methyl Ester" @default.
• W2117582597 cites W1613436034 @default.
• W2117582597 cites W1963591519 @default.
• W2117582597 cites W1964445501 @default.
• W2117582597 cites W1964823195 @default.
• W2117582597 cites W1967000579 @default.
• W2117582597 cites W1967266228 @default.
• W2117582597 cites W1967840499 @default.
• W2117582597 cites W1972295774 @default.
• W2117582597 cites W1977588727 @default.
• W2117582597 cites W1977602563 @default.
• W2117582597 cites W1977950783 @default.
• W2117582597 cites W1979640190 @default.
• W2117582597 cites W1980947232 @default.
• W2117582597 cites W1980971736 @default.
• W2117582597 cites W1982504463 @default.
• W2117582597 cites W1986233198 @default.
• W2117582597 cites W1988983889 @default.
• W2117582597 cites W1993289104 @default.
• W2117582597 cites W1994524513 @default.
• W2117582597 cites W1995448283 @default.
• W2117582597 cites W1997458480 @default.
• W2117582597 cites W1998305107 @default.
• W2117582597 cites W2003131213 @default.
• W2117582597 cites W2003222067 @default.
• W2117582597 cites W2006552313 @default.
• W2117582597 cites W2009124746 @default.
• W2117582597 cites W2010046098 @default.
• W2117582597 cites W2010633578 @default.
• W2117582597 cites W2011578272 @default.
• W2117582597 cites W2011936860 @default.
• W2117582597 cites W2012933160 @default.
• W2117582597 cites W2017223027 @default.
• W2117582597 cites W2018253917 @default.
• W2117582597 cites W2020863464 @default.
• W2117582597 cites W2022412731 @default.
• W2117582597 cites W2023024682 @default.
• W2117582597 cites W2023794597 @default.
• W2117582597 cites W2024748066 @default.
• W2117582597 cites W2025006912 @default.
• W2117582597 cites W2026207420 @default.
• W2117582597 cites W2026926851 @default.
• W2117582597 cites W2027845695 @default.
• W2117582597 cites W2028045289 @default.
• W2117582597 cites W2029321142 @default.
• W2117582597 cites W2035525291 @default.
• W2117582597 cites W2037588333 @default.
• W2117582597 cites W2040290625 @default.
• W2117582597 cites W2042602320 @default.
• W2117582597 cites W2044673682 @default.
• W2117582597 cites W2044852418 @default.
• W2117582597 cites W2045463233 @default.
• W2117582597 cites W2046236540 @default.
• W2117582597 cites W2048407273 @default.
• W2117582597 cites W2050464496 @default.
• W2117582597 cites W2055264554 @default.
• W2117582597 cites W2057063691 @default.
• W2117582597 cites W2057164485 @default.
• W2117582597 cites W2057332886 @default.
• W2117582597 cites W2058623521 @default.
• W2117582597 cites W2059373941 @default.
• W2117582597 cites W2059746967 @default.
• W2117582597 cites W2067272205 @default.
• W2117582597 cites W2072197372 @default.
• W2117582597 cites W2074632092 @default.
• W2117582597 cites W2077065089 @default.
• W2117582597 cites W2077204658 @default.
• W2117582597 cites W2082275305 @default.
• W2117582597 cites W2082746388 @default.
• W2117582597 cites W2083606740 @default.
• W2117582597 cites W2084570493 @default.
• W2117582597 cites W2087166091 @default.
• W2117582597 cites W2092658289 @default.
• W2117582597 cites W2092683059 @default.
• W2117582597 cites W2094855248 @default.
• W2117582597 cites W2094871139 @default.
• W2117582597 cites W2099055074 @default.
• W2117582597 cites W2100959093 @default.
• W2117582597 cites W2105756184 @default.
• W2117582597 cites W2105879297 @default.
• W2117582597 cites W2109261012 @default.
• W2117582597 cites W2110506537 @default.
• W2117582597 cites W2112766781 @default.
• W2117582597 cites W2115555537 @default.
• W2117582597 cites W2118259080 @default.
• W2117582597 cites W2119514011 @default.
• W2117582597 cites W2126022387 @default.
• W2117582597 cites W2127415785 @default.
• W2117582597 cites W2134218364 @default.

• next