- Stereoselective synthesis of (3R,6S)-6-hydroxylasiodiplodin
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The first stereoselective synthesis of polyketide natural product (3R,6S)-6-hydroxylasiodiplodin (1) has been described starting from commonly available starting materials d-mannitol and 2,4,6-trihydroxybenzoic acid. The key reactions involved are Keck asymmetric allylation, Stille coupling, De Brabander's esterification, and ring-closing metathesis (RCM) reaction. The total synthesis was achieved in 19.3% overall yield making the route significant.
- Bujaranipalli, Sheshurao,Das, Saibal
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supporting information
p. 1653 - 1655
(2016/04/04)
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- Stereoselective total synthesis of cananginones (D-I) using Ireland-Claisen rearrangement as a key step
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A strategy for stereoselective total synthesis of α-substituted γ-hydroxymethyl γ-butyrolactone containing bioactive natural products cananginones (D-I) has been developed using cheap and commercially available d-mannitol as a chiral pool. The Ireland-Cla
- Kuilya, Tapan Kumar,Chatterjee, Shamba,Goswami, Rajib Kumar
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p. 2905 - 2918
(2014/04/17)
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- Total synthesis of diastereomeric marine butenolides possessing a syn-aldol subunit at C10 and C11 and the related C11-ketone
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Two diastereomeric marine butenolides, (4S,10R,11R)- and (4S,10S,11S)-4,11-dihydroxy-10-methyldodec-2-en-1,4-olide, possessing a syn-aldol subunit at C10 and C11 have been efficiently synthesized by using a three-module coupling strategy. The enantiomeric syn-aldol modules prepared by the syn-selective aldol reaction of the norephedrine-derived chiral propionates were coupled with the chiral C3-C7 module via 1,3-dithiane bisalkylation. The butenolide ring was then installed via a high-yielding ring-closing metathesis (RCM) reaction. Oxidation of the diastereomeric C11-alcohols furnished the corresponding C11-ketones, which are produced by the same marine microorganism.
- Wang, Yan,Dai, Wei-Min
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supporting information; scheme or table
p. 187 - 196
(2010/03/04)
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- Total synthesis of nonenolide
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A novel synthetic route has been reported for the synthesis of nonenolide. The syntheses of fragments were initiated from commercially available and inexpensive starting materials. The synthesis involves key steps like Sharpless epoxidation, Jacobsen's re
- Meshram, Harshadas Mitaram,Kumar, Dachepally Aravind,Ramesh, Palakuri
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scheme or table
p. 1422 - 1427
(2010/09/12)
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- The formal synthesis of isofebrifugine using stereoselective intramolecular Michael addition
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The formal synthesis of isofebrifugine, a bioactive alkaloid, was achieved via a stereoselective intramolecular Michael addition reaction from d-mannitol.
- Sudhakar, Neela,Srinivasulu, Gannoju,Rao, Ganipisetti Srinivas,Rao, Batchu Venkateswara
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experimental part
p. 2153 - 2158
(2009/04/05)
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- Asymmetric total synthesis of martinelline and martinellic acid
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Herein, we describe the first asymmetric total synthesis of (-)-martinelline ((-)-2) and the second total synthesis of (-)-martinellic acid ((-)-1) by employing a tandem Mukaiyama-Mannich reaction/aminal cyclization as the key step. The Royal Society of C
- Ikeda, Shuhei,Shibuya, Masatoshi,Iwabuchi, Yoshiharu
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p. 504 - 506
(2007/10/03)
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- Stereoselective synthesis of chiral tetrahydrofurans with potent 5-LO inhibitory activity
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Chiral glyceraldehydes have been exploited for the design of convenient and scalable synthetic approaches to chiral tetrahydrofurans, which have potential as potent 5-lipoxygenase (5-LO) inhibitors. The synthesis of all four possible stereoisomers by a general methodology is reported; wherein the chirons derived from the glyceraldehyde derivatives on reaction with homopropargyl ether, cyclization and further reactions gave the targets.
- Sharma,Punna, Sreenivas,Krishna, Palakodety Radha,Chorghade, Mukund S.,Ley, Steven V.
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p. 1125 - 1133
(2007/10/03)
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- Stereoselective syntheses of pharmaceutically relevant chiral tetrahydrofurans from (S)- and (R)-glyceraldehyde derivatives
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A practically simple and flexible method of making chiral tetrahydrofurans of therapeutic relevance is reported from glyceraldehyde derivatives as chiral synthons. One of the stereocentres is derived from glyceraldehyde derivatives, while the other one is introduced by Sharpless asymmetric epoxidation using either (+)- or (-)-DIPT.
- Sharma,Punna, Sreenivas,Rajendra Prasad,Krishna, Palakodety Radna,Chorghade, Mukund S.,Ley, Steven V.
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p. 1113 - 1123
(2007/10/03)
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- Stereoselective synthesis of (+)-SCH 351448: A unique ligand system for sodium, calcium, and other cations
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(+)-SCH 351448 (Na+ salt A) was synthesized employing ring-closing olefin metathesis reaction of an open diene diester intermediate for construction of the 28-membered macrodiolide structure. The open diene diester was prepared from the monomeric hydroxy carboxylic acid and two different olefin fragments. The monomeric hydroxy acid was synthesized via Julia-Julia coupling reaction of intermediates derived from the same olefinic fragments. Oxane units in these fragments were prepared by radical cyclization reactions of β-alkoxyacrylates. Analogous SCH 351448 salts incorporating other mono- and divalent cations may be prepared. Under acidic conditions, SCH 351448 (Na+ salt A) was the most stable complex, but SCH 351448 (Ca2+ salt) and (Na+ salt B) appear to be physiologically important species.
- Kang, Eun Joo,Cho, Eun Jin,Ji, Mi Kyung,Lee, Young Eun,Shin, Dong Mok,Choi, Soo Young,Chung, Young Keun,Kim, Jong-Seo,Kim, Hie-Joon,Lee, Sueg-Geun,Lah, Myoung Soo,Lee, Eun
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p. 6321 - 6329
(2007/10/03)
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- Reductive spiroannulation of nitriles with secondary electrophiles
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(Chemical Equation Presented) The scope of reductive decyanation and spiroannulation reactions has been expanded to include secondary electrophiles for potentially useful transformations. Secondary phosphates and chlorides, as well as terminal epoxides, c
- Morin, Matthew D.,Rychnovsky, Scott D.
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p. 2051 - 2053
(2007/10/03)
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- Synthesis of the spiroacetal fragment of broussonetine H
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(2S,6S)-2-(3-Bromopropyl)-1,7-dioxaspiro[5.5]undecane 3 was prepared by the addition of the acetylide derived from (4S)-4-benzyloxy-7-tert-butyldiphenylsilyloxyhep-1-yne 8 to δ-valerolactone 6 followed by treatment with hydrogen and palladium on charcoal which effected hydrogenation of the alkyne, hydrogenolysis of the benzyl ether and subsequent spiroacetal formation. The (4S)-stereochemistry in acetylene 8 was established by addition of trimethylsilylacetylene 10 to (2S)-epoxide 9, which in turn is derived from L-glutamic acid 11.
- Brimble, Margaret A.,Park, Jae H.,Taylor, Carol M.
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p. 5861 - 5868
(2007/10/03)
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- Synthesis of the core structure of apicularen a by transannular cyclization.
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[reaction: see text] An approach to the macrocyclic core of apicularen A is described. Thus, cross-coupling of the aryl triflate 7 with the vinylstannane 19 provided the styrene 20. Deprotection led to the dihydroxy acid 22. Through a size-selective macro
- Kuehnert, Sven M,Maier, Martin E
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p. 643 - 646
(2007/10/03)
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- A synthesis of (-)-tashiromine and formal synthesis of (+)-tashiromine utilizing a highly enantioselective pyrrole/cobaloxime π-cation cyclization
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Cyclization of (5-N-pyrrolyl-2-hydroxypentyl)cobaloxime (13) proceeds by intramolecular electrophilic aromatic substitution of a cobaloxime π-cation onto the pyrrole ring to provide 6-exo cyclization product (14) in 95% yield. This cyclization is highly enantioselective. It is applied to a synthesis of highly enantioenriched (-)-tashiromine, (-)-21, and a formal synthesis of (+)-tashiromine.
- Gage, Jennifer L.,Branchaud, Bruce P.
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p. 7007 - 7010
(2007/10/03)
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- Studies directed towards the synthesis of clonostachydiol - Part I
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A strategy was developed for the first total synthesis of clonostachydiol which inturn would assign the absolute configuration, based on the chiron approach, using carbohydrate derived chiral synthons.This study however culminated in the synthesis of (2R,
- Rao, A. V. Rama,Murthy, V. S.,Sharma, G. V. M.
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p. 139 - 142
(2007/10/02)
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- Functionalized Diorganozinc Compounds: Key Reagents for the Synthesis of Enantiomerically Pure 2,5-Disubstituted cis- and trans-Tetrahydrofurans
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1,4-Diol derivatives 4a-i were synthesized stereoselectively by either reagent- or catalyst-controlled routes using the addition of functionalized diorganozinc reagents to aldehydes.The stereoselectivities along the reagent-controlled synthetic path were in the range between 80:20 and 95:5.The stereoselectivities along the catalyst route exceeded 95:5.The 1,4-diol derivatives 4 thus obtained were transformed into enantiomerically pure cis- and trans-2,5-disubstituted tetrahydrofurans (16-20) by means of an intramolecular Williamson reaction. - Keywords: Synthesis, stereoselective / Catalysis / Tetrahydrofurans / Dialkylzinc reagents
- Berninger, Joern,Koert, Ulrich,Eisenberg-Hoehl, Christina,Knochel, Paul
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p. 1021 - 1028
(2007/10/03)
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- Total synthesis of (+)-rolliniastatin 1
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The first total synthesis of the naturally occurring acetogenin (+)-rolliniastatin 1 (1) has been achieved. A high degree of stereochemical control in the construction of the bis-THF system was accomplished by chelation controlled addition of functionalized organo-metallic reagents derived from 5 and 11 to α-alkoxy-aldehydes.
- Koert
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p. 2517 - 2520
(2007/10/02)
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- The Synthesis of Optically Pure Epoxyalkyl β-D-Glucosides and β-Cellobiosides as Active-Site Directed Inhibitors of Some β-Glucan Hydrolases
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(2R)- and (2S)-2,3-Epoxypropyl, (3R)- and (3S)-3,4-epoxybutyl and (4S)-4,5-epoxypentyl β-D-glucopyranoside, together with the (3R)- and (3S)-3,4-epoxybutyl β-cellobioside, have been prepared by condensation of a glycosyl bromide with the appropriate enantiomer of a chiral alcohol containing a diol protected as an isopropylidene acetal, and subsequent manipulation of the unmasked diol to the epoxide function.As well, in an improvement to the whole process, both diastereoisomers of the various epoxypropyl and epoxybutyl glycosides were available, from just the one enantiomer of the alcohol by an alternative manipulation of the diol.Finally, precursors to 2,3-epoxy-4-hydroxybutyl β-D-glucosides and β-cellobiosides were prepared in high optical purity by Sharpless asymmetric epoxidation of the appropriate 4-hydroxybutyl-2-enyl glycosides.
- Rodriguez, Evelyn B.,Scally, Gavin D.,Stick, Robert V.
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p. 1391 - 1405
(2007/10/02)
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- Stereoselective Reduction of Bicyclic Ketals. A New, Enantioselective Synthesis of Isolaurepinnacin and Lauthisan Skeletons
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A general synthetic strategy for constructing seven- and eight-membered cyclic ether derivatives is described.The important feature of this work is a highly stereoselective reduction of bicyclic ketals, i.e., cis-selective reduction with triethylsilane/TiCl4 and trans-selective reduction with diisobutylaluminum hydride (DIBAL).The procedure completed a new and efficient synthesis of isolaurepinnacin and lauthisan skeletons in optically active forms.
- Kotsuki, Hiyoshizo,Ushio, Yasuyuki,Kadota, Isao,Ochi, Masamitsu
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p. 5153 - 5161
(2007/10/02)
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- SYNTHESE ENANTIOSPECIFIQUE DU 5-HEXADECANOLIDE, PHEROMONE DE "VESPA ORIENTALIS"
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A synthetic scheme was elaborated to prepare (R)(+) δ-n-hexadecanolactone 10 in 8 steps from (L)-glutamic acid.
- Larcheveque, Marc,Lalande, Julien
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p. 1061 - 1066
(2007/10/02)
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