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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
31

Synthetic Approaches To Herbertenoid And Cuparenoid Sesquiterpenes

Ravikumar, P C 08 1900 (has links)
Among Nature's creation, terpenoids are more versatile and exciting natural products. In a remarkable display of synthetic ingenuity and creativity, nature has endowed terpenes with a bewildering array of carbocyclic frameworks with unusual assemblage of rings and functionalities. This phenomenal structural diversity of terpenes makes them ideal targets for developing and testing new synthetic strategies for efficient articulation of carbocyclic frameworks. The thesis entitled “Synthetic Approaches to Herbertenoid and Cuperenoid Sesquiterpenes" describes the application of ring-closing metathesis and Claisen rearrangement based approach to some herbertenoid and cuparenoid natural products. The results are described in five different sections, viz., a) First Total Synthesis of (±)-γ-Herbertenol; b) First Total Synthesis of (±)-HM-2; c) First Total Synthesis of (±)-HM-4 and HM-3; d) First Total Synthesis of Herbertenones A and B; and e) Total Synthesis of Lagopodin A. Complete details of the experimental procedures and the spectroscopic data were provided in a different section. A brief introduction is provided wherever appropriate to keep the present work in proper perspective. The compounds are sequentially numbered (bold), references are marked sequentially as superscripts and listed in the last section of the thesis. All the spectra included in the thesis were obtained by xeroxing the original NMR spectra. To begin with, the first total synthesis of γ-herbertenol, an herbertene isolated from a non-herbertus source, has been accomplished starting from 3,5-dimethylphenol. Claisen rearrangement of 3-(3-methoxy-5-methylphenyl)but-2-en-1-ol, obtained in eight steps from 3,5-dimethylphenol, furnished a γ,δ-unsaturated ester, which was transformed into 4-aryl-4,5,5-trimethylcyclopent-2-enone employing RCM reaction as the key step, which was further transformed into (±)-γ-herbertenol, which exhibited spectral data identical to that of the natural product. An alternative RCM reaction based methodology was also developed for the synthesis of γ-herbertenol methyl ether starting from ethyl 3-aryl-3-methylpent-4-enoate, an intermediate in the first sequence. The methodology has been extended for the synthesis of the putative structure of HM-2 starting from 2,4-dimethoxy-5-methylacetophenone via the corresponding ethyl 3-aryl-3-methylpent-4-enoate. However, the spectral data of the synthetic compound was found to be different from that reported for the natural product. A new cuperenoid structure for HM-2 was proposed. Total synthesis of cuparene-1,4-diol starting from toluhydroquinone, followed by its conversion to mono methyl ether and mono acetyl derivative confirmed the structures of HM-1 and the revised structure of HM-2. In a similar manner, total synthesis of the putative structure of HM-3 starting from 4-methylresorcinol dimethyl ether proved it to be wrong. A cupereniod structure, HM-4 monoacetate was proposed for HM-3. Synthesis of HM-4, and its conversion to mono acetate confirmed the structures of HM-4 and the revised structure of HM-3. The methodology has been further extended to the first total synthesis of herbertenones A and B starting from 2,5-dimethoxybenzaldehyde. By readily identifying the similarity between lagopodin A and HM-1 and HM-2, an intermediate in the synthesis of HM-1 and HM-2 has been further transformed in to (±)lagopodin A.
32

Enantioselective Total Synthesis Of Diverse, Bioactive Natural Products : (+)-1S-Minwanenone, (+)-SCH 642305 And 6-EPI-(-)-Hamigeran B

Murlidhar, Shinde Harish 07 1900 (has links)
Natural product synthesis is one of the most creative branch of chemistry in terms of its boundless scope for innovation and has stimulated several generations of synthetic organic chemists. With advancement in the technology, particularly in the isolation and purification techniques, high-field NMR and X-ray crystallography, it has become fairly routine to isolate and assign the structures, high-field NMR and X-ray crystallography, it has become fairly routine to isolate and assign the structures, even to those complex molecules, which are available only in microscopic quantities from natural sources. Concurrently, one has witnessed tremendous advances in the availability of new synthetic methodologies with high region-, stereo-, and enantiocontrol for one or multiple C-C bond formations and rapid generation of molecular complexity. These developments have rekindled interest with total synthesis of natural products as platforms for testing and validating new reactions and strategies. Many natural products exhibit wide range of biological activities and thus provide good leads in drug discovery but quite often such bioactive compounds are obtained only in minute quantities from Nature. Hence, there is need to synthesize them to obtain requisite quantities and build diversity around their scaffold to further explore their therapeutic potential. Thus, natural product synthesis combines both intellectual challenge and possible application for human wellbeing. Our research group is actively engaged in the synthesis of structurally complex, bioactive natural products and as a part of this endeavour, total syntheses of several bioactive compounds have been accomplished in our laboratory in recent past. The present thesis has also evolved around the ongoing theme directed towards natural product synthesis and is organized under three chapters. Chapter I: Total synthesis of (+)-1S-Minwanenone Chapter II: Enantioselective total synthesis of the bioactive natural product (+)-Sch 642305. Chapter III: Enantiospecific total synthesis of 6-epi-(-)-Hamigeran B.
33

Total Synthesis of Bio-Active Macrolide Natural Products and Sulfinamide Based Ligands in Asymmetric Catalysis

Revu, Omkar January 2015 (has links) (PDF)
The thesis entitled “Total synthesis of bio-active macrolide natural products and sulphonamide based ligands in asymmetric catalysis” is divided into two chapters. First chapter of the thesis describes the total synthesis of bio-active macrolide natural products cladospolide A 1, seimatopolide A 2 and synthetic studies towards aetheramides A 3 and B 4 (Figure 1). Figure 1: Bio-active macrolide natural products. Section A of chapter 1 describes the enantiospecific total synthesis of cladospolide A (ent-1). Cladospolide A was isolated from three different sources such as culture filtrate of cladosporium fulvam FI-113, Fungus cladosporium tenuissimum and Fermentation broath of cladosporium sp. FT-0012. Cladospolide A is shown to inhibit the root growth of lettuce seedlings. Enantiospecific total synthesis of cladospolide A ent-1 was accomplished in 9% overall yield in 11 linear steps using D-ribose as a chiral pool precursor. Key reactions in the present approach include olefin cross metathesis and Yamaguchi macrolactonization reactions (Scheme 1). Scheme 1: Total synthesis of cladospolide A (ent-1). Section B of chapter 1 describes the use of furan as a surrogate for the E-but-2-ene-1, 4-dione unit in the total synthesis of seimatopolide A 2. Seimatopolide A 2 was isolated by Heip and co-workers from the fungus Seimatosporium discosioides in 2012 and is shown to activate the γ-subtype peroxysome proliferator-activated receptors (PPAR-γ), which is a pivotal process in the type-2 diabetes. Total synthesis of ent-seimatopolide A was accomplished in 7.8% overall yield in 14 linear steps from furfural. Nagao acetate aldol and Shiina macrolactonization reactions were employed as key reactions for the synthesis of ent-seimatopolide A (ent-2) (Scheme 2). Scheme 2: Stereoselective total synthesis of seimatopolide A (ent-2). In section C of Chapter 1, studies towards the synthesis of aetheramides A 3 and B 4 are described. Aetheramides A 3 and B 4 are isolated by Müller’s group in 2012 from the novel myxobacterial genus “Aetherobacter”. Aetheramides are cyclic depsipeptides, which are shown to inhibit the HIV-I infection with IC50 values of ∼0.015 μM and cytostatic activity against human colon carcinoma (HCT-116) cells with IC50 values of 0.11 μM. Stereochemistry at two chiral centers present in the molecules is unassigned. The first approach (Scheme 3) relied on macrolactonization as the key step while the second approach (Scheme 4) relied on RCM to accomplish the macrolactonization. The required precursors were synthesized from elaboration of chiral furyl carbinol, while synthesis of the RCM precursor was accomplished employing the aldol reaction. Scheme 3: Macrolactonization strategy for synthesis of 3 from chiral furyl carbinol. Scheme 4: RCM strategy for synthesis of 3 from chiral furyl carbinol. The successful synthesis of the macrolactone core of aetheramide A 1 is accomplished by employing the ring closing metathesis reaction to construct the C18-C19 bond. RCM precursor has been synthesized by the amidation of the amine derived from R-mandelic acid, while the acid fragment is synthesized from allyl trityl ether (Scheme 5). Scheme 5: RCM strategy for synthesis of 3 from R-mandelic acid. Second chapter of the thesis describes the synthesis and application of novel sulfinamide ligands in asymmetric catalysis. In section A of chapter 2, chiral 2-pyridylsulfinamides are shown to be effective catalysts in the alkylation of aryl and alkyl aldehydes with diethylzinc providing the corresponding alcohols in excellent enantioselectivity. It was found that the chirality present at sulfur in the ligand is pivotal for the asymmetric induction (Scheme 6). Scheme 6: Asymmetric alkylation of benzaldehyde with some of the 2-Pyridyl sulfinamide catalysts. Second section of chapter 2 describes the synthesis and application of C2-symmetric bis-sulfinamides in Rh (I) catalyzed conjugate addition of PhB(OH)2 to enones. Chirality present at sulphur in sulfonamide as well as symmetry present in the ligand plays crucial role in the outcome of the reaction (Scheme 7). Scheme 7: Asymmetric arylation of enones using C2-symmetric bis-sulfinamide/olefin ligands. The thesis entitled “Total synthesis of bio-active macrolide natural products and sulphonamide based ligands in asymmetric catalysis” is divided into two chapters. First chapter of the thesis describes the total synthesis of bio-active macrolide natural products cladospolide A 1, seimatopolide A 2 and synthetic studies towards aetheramides A 3 and B 4 (Figure 1). Figure 1: Bio-active macrolide natural products. Section A of chapter 1 describes the enantiospecific total synthesis of cladospolide A (ent-1). Cladospolide A was isolated from three different sources such as culture filtrate of cladosporium fulvam FI-113, Fungus cladosporium tenuissimum and Fermentation broath of cladosporium sp. FT-0012. Cladospolide A is shown to inhibit the root growth of lettuce seedlings. Enantiospecific total synthesis of cladospolide A ent-1 was accomplished in 9% overall yield in 11 linear steps using D-ribose as a chiral pool precursor. Key reactions in the present approach include olefin cross metathesis and Yamaguchi macrolactonization reactions (Scheme 1). Scheme 1: Total synthesis of cladospolide A (ent-1). Section B of chapter 1 describes the use of furan as a surrogate for the E-but-2-ene-1, 4-dione unit in the total synthesis of seimatopolide A 2. Seimatopolide A 2 was isolated by Heip and co-workers from the fungus Seimatosporium discosioides in 2012 and is shown to activate the γ-subtype peroxysome proliferator-activated receptors (PPAR-γ), which is a pivotal process in the type-2 diabetes. Total synthesis of ent-seimatopolide A was accomplished in 7.8% overall yield in 14 linear steps from furfural. Nagao acetate aldol and Shiina macrolactonization reactions were employed as key reactions for the synthesis of ent-seimatopolide A (ent-2) (Scheme 2). Scheme 2: Stereoselective total synthesis of seimatopolide A (ent-2). In section C of Chapter 1, studies towards the synthesis of aetheramides A 3 and B 4 are described. Aetheramides A 3 and B 4 are isolated by Müller’s group in 2012 from the novel myxobacterial genus “Aetherobacter”. Aetheramides are cyclic depsipeptides, which are shown to inhibit the HIV-I infection with IC50 values of ∼0.015 μM and cytostatic activity against human colon carcinoma (HCT-116) cells with IC50 values of 0.11 μM. Stereochemistry at two chiral centers present in the molecules is unassigned. The first approach (Scheme 3) relied on macrolactonization as the key step while the second approach (Scheme 4) relied on RCM to accomplish the macrolactonization. The required precursors were synthesized from elaboration of chiral furyl carbinol, while synthesis of the RCM precursor was accomplished employing the aldol reaction. Scheme 3: Macrolactonization strategy for synthesis of 3 from chiral furyl carbinol. Scheme 4: RCM strategy for synthesis of 3 from chiral furyl carbinol. The successful synthesis of the macrolactone core of aetheramide A 1 is accomplished by employing the ring closing metathesis reaction to construct the C18-C19 bond. RCM precursor has been synthesized by the amidation of the amine derived from R-mandelic acid, while the acid fragment is synthesized from allyl trityl ether (Scheme 5). Scheme 5: RCM strategy for synthesis of 3 from R-mandelic acid. Second chapter of the thesis describes the synthesis and application of novel sulfinamide ligands in asymmetric catalysis. In section A of chapter 2, chiral 2-pyridylsulfinamides are shown to be effective catalysts in the alkylation of aryl and alkyl aldehydes with diethylzinc providing the corresponding alcohols in excellent enantioselectivity. It was found that the chirality present at sulfur in the ligand is pivotal for the asymmetric induction (Scheme 6). Scheme 6: Asymmetric alkylation of benzaldehyde with some of the 2-Pyridyl sulfinamide catalysts. Second section of chapter 2 describes the synthesis and application of C2-symmetric bis-sulfinamides in Rh (I) catalyzed conjugate addition of PhB(OH)2 to enones. Chirality present at sulphur in sulfonamide as well as symmetry present in the ligand plays crucial role in the outcome of the reaction (Scheme 7). Scheme 7: Asymmetric arylation of enones using C2-symmetric bis-sulfinamide/olefin ligands.
34

Enantiospecific Synthesis Of DI- and Linear Triquinanes

Janardhan, Ghodke Neetu January 2012 (has links) (PDF)
Employing a chiral pool strategy, enantiospecific syntheses of di- and triquinanes have been accomplished. α-Campholenaldehyde 95, readily available from the abundantly available monoterpene α-pinene 94, has been utilised as the chiral starting material. To begin with, enantiospecific synthesis of the diquinane 134 has been developed employing Nazarov cyclisation of the cross-conjugated dienone 132 as the key reaction (Scheme 37).71 Synthesis of the dienone 132 was accomplished by selenium dioxide mediated oxidation of the olefinic methyl group in α-campholenyl methyl ether 130, followed by further elaboration of the resultant aldehyde 131. OMe P2O5 MsOH The Nazarov cyclisation strategy has been further extended, as depicted in Scheme 38, for the synthesis of the triquinane enones 145 and 146 via the cross conjugated enone 144.71 The dienone 144 was obtained from the diquinane 136, which is readily available from campholenaldehyde 95 via an intramolecular rhodium carbenoid CH insertion reaction. Of the three methyl groups in campholenaldehyde 95, the olefinic methyl group can easily be functionalised, for example, via allylic oxidation. However, the remaining two tertiary methyl groups are difficult to functionalise, and there is no report in the literature on the utility of these two gem dimethyl groups either for functionalisation or for further elaboration, and remained only as gem dimethyl group in the products. It was conceived that it could be possible to utilise the tertiary methyl carbon for the ring construction via an intramolecular rhodium carbenoid γ-CH insertion reaction. To test the hypothesis, campho¬lenaldehyde 95 was converted into the diazoketone 165. Treatment of the diazoketone 165 with a catalytic amount of rhodium acetate furnished the diquinane 166, via a highly regio-and stereoselective insertion of the intermediate rhodium carbenoid in the CH bond of the tertiary methyl group, which is located cis with respect to the diazoketone, Scheme 39.72 As an application of the Nazarov cyclisation mediated synthesis of the diquinane 134, enantiospecific synthesis of the analogues of capnellenes, ABC and ABD ring systems of aberraranes have been carried out. A methyl cuprate reaction on the enone 134 generated the key intermediate, the ketone 169. A ring-closing metathesis (RCM) based cyclo¬pentannulation has transformed the diquinane 169 into the analogue of capnellene 175, as well as the analogue 197 of the ABC ring system of aberrarane. On the other hand, a Wacker reaction-intramolecular aldol condensation based spirocyclohexannulation transformed the diquinane 169 into an analogue 201 of the ABD ring system of aberrarane, Scheme 40.73 Finally, degradation of the two additional carbon atoms present on the A-ring furnished the ABC and ABD ring systems 235 and 238 of aberrarane, Scheme 41.(For structural formula pl refer the abstract pdf file)
35

Total Synthesis Of Bio-active Oxylipins And Diyne Containing Natural Products

Swain, Bandita 03 1900 (has links) (PDF)
Total synthesis of natural products is of contemporary interest in organic synthesis. One of the useful ways to synthesize the natural products is to originate from inexpensive chiral pool compounds abundantly available in nature. In this context, our research group is actively involved in the use of tartaric acid as the four carbon four hydroxy building block in the synthesis of a number of natural products of therapeutic importance. Our strategy relies on the utility of γ-hydroxy amides derived from tartaric acid involving a controlled addition of Grignard reagents and stereoselective reduction. We were successful in application o f this useful building block for the synthesis of a variety of natural products possessing varied functional groups (Chart-1). derived from tartaric acid in the synthesis of oxylipins such as pinellic acid and diyne containing natural products. Chapter 1 of the thesis describes the total synthesis of (+) pinellic acid 6 and (Z,8S,9S,10R)-8,9,10-trihydroxyoctadec-6-enoic acid 10. Key strategy in the synthesis of pinellic acid is elaboration of the aldehyde 3, derived from the γ-hydroxy amide 2 via Horner-Emmons-Wadsworth reaction to yield the α,β-unsaturated ketone 4. Stereoselective reduction of the ketone with (R)-BINAL-H produced the alcohol with requisite stereochemistry which was further extended to pinellic acid 6 (Scheme 1). Wittig homologation of the aldehyde 8 derived from γ-hydroxy amide 7 is the key step for the synthesis of the (Z,8S,9S,10R)-8,9,10-trihydroxyoctadec-6-enoic acid 10. Second chapter of the thesis deals with total synthesis of diyne containing natural products. In the first part of this chapter enantioselective synthesis of possible diastereomers of heptadeca1-ene-4,6-diyne-3,8,9,10-tetrol, a structure proposed for the natural product isolated from Hydrocotyle leucocephala, is accomplished. The alkyne precursors 13 and 14 were synthesized from the α-hydroxy ester 12 derived from γ-hydroxy amide 11 while the alkyne 17 is synthesized from the masked tetrol 16 derived from lactol 15 which was obtained from D-ribose. yne to assemble the diyne unit which was further elaborated to heptadeca-1-ene-4,6-diyne3,8,9,10-tetrol (Scheme 3). It was found that the NMR spectral data of the putative structure assigned for the natural product did not match with any of the diasteromers that were synthesized. This establishes that the structure proposed for the natural product is wrong and requires revision. OH OH OH 18 OH OH 19 OH OH 20 OH OH Scheme 3: Synthesis of diastereomers of heptadeca-1-ene-4,6-diyne-3,8,9,10-tetrol. [Part of this work is published: Prasad, K. R.; Swain, B. J. Org. Chem. (in press)] Second part of this chapter deals with the synthesis of panaxytriol 26 and panaxydiol 28. Key reaction in the synthesis of panaxytriol and panaxdiol is the coupling of bromoalkynes 25 and 27 with 3-silyloxy pent-1-en-4-yne and further elaboration to the triol and diol. The required alkynes were synthesized from the primary alcohol 24 which was obtained from the γ-hydroxy amide 11 involving a series of simple synthetic operations. (Scheme 4). (For structural formula pl see the abstract file)
36

Studies towards the total synthesis and structure elucidation of leiodolide A

Mould, Katy M. January 2013 (has links)
Leiodolide A is a unique natural product isolated from Pacific marine sponges which has provided an interesting target for total synthesis due to its complex structure and undefined stereochemistry. Although synthetic work towards the synthesis of sister compound leiodolide B has been published, the total synthesis of leiodolide A is yet to be achieved but remains an important target due to high potency against leukaemia, non-small lung and ovarian cancers. The convergent strategy towards the synthesis of leiodolide A involved the synthesis of three subunits; a synthetic route to the C21-C25 vinyl stannane is described, and efforts towards the synthesis of the bidirectional C11-C20 subunit are detailed. Asymmetric vinylogous aldol methodology was developed for the installation of the 1,2-syn propionate motif found in the C1-C10 subunit and in other polypropionate natural products, and was shown to be applicable to a range of substrates in moderate diastereoselectivity and excellent enantioselectivity.
37

Enantiospecific Total Synthesis of Phomopsolide B, Macrosphelides A & E and Total Synthesis & Determination of Absolute Configuration of Synargentolide B

Gutala, Phaneendra January 2013 (has links) (PDF)
Section I of the thesis deals with the enantiospecific total synthesis of phomopsolide B. Phomopsolide B was isolated from a strain of Phomopsis Oblonga. Enantiospecific total synthesis of phomopsolide B was accomplished in 13 overall yield in 12 linear steps using (S)-lactic acid and L-tartaric acid as chiral pool precursors. Present approach involves the efficient use of -keto phosphonate derived from commercially available (S)-ethyl lactate. Horner-Wadsworth-Emmons reaction and Still-Gennari olefination were employed as key reactions in the synthesis (scheme 1). Scheme 1: Total synthesis of phomopsolide B. [This work has been published: Prasad, K. R.; Gutala, P. Tetrahedron 2012, 68, 7489-7493.] Section II of the thesis describes the total synthesis of macrosphelides A and E which are isolated from a culture broth of Microsphaeropsis sp. FO-5050 and from the strain Periconia byssoides. Total synthesis of macrosphelides A and E was accomplished in 19 overall yield from commercially available (S)-ethyl lactate. Horner-Wadsworth-Emmons reaction and Yamaguchi lactonization were employed as key reactions for the total synthesis of macrosphelides A and E (scheme 2). Scheme 2: Total synthesis of macrosphelides A and E. [This work has been published: Prasad, K. R.; Gutala, P. Tetrahedron 2011, 67, 4514-4520.] Section III of the thesis deals with total synthesis and determination of absolute configuration of synargentolide B 1. Synargentolide B 1 is a 5,6-dihydro--pyrone containing natural product and was isolated from Syncolostemon Argenteus by Rivett et al. in 1998 (fig 1). The relative stereochemistry at C-6, C-6′ positions in synargentolide B 1 was assigned to be R, S respectively based on the positive cotton effect in the CD spectrum. Threo stereochemistry was proposed for the C1′-C2′ diol unit in synargentolide B 1 based on the NMR studies. The stereochemistry at C-5 could not be assigned, hence the structure of synargentolide B 1 was tentatively proposed as 6R-[5,6S-(diacetyloxy)-1,2-(dihydroxy)-3Eheptenyl]-5,6-dihydro-2H-pyran-2-one (fig. 1). Figure 1: Putative structure of synargentolide B 1. Based on the tentative stereochemistry at the C-6, C-6′ positions proposed by Rivett et al. and taking into consideration the threo relationship for the C-1′-C-2′ diol unit, it is anticipated that the structure of synargentolide B 1 could be one of the four possible diastereomers 1a-1d (fig 2). Figure 2: Possible diastereomers of synargentolide B (1a-d). Incidentally, one of the diastereomers 6R-[5R,6S-(diacetyloxy)-1S,2R-(dihydroxy)- 3E-heptenyl]-5,6-dihydro-2H-pyran-2-one 1d was a reported natural product isolated in 1990 from Hyptis oblangifolia by Pereda-Miranda, R. et al. along with its corresponding diacetylated product 2 (fig 3). Fig. 3: Natural products isolated from Hyptis oblangifolia by Pereda-Miranda, R. et al. Total synthesis and determination of absolute configuration of synargentolide B 1 were accomplished by synthesizing four possible diastereomers of the natural product (1a-1d) and by comparison of the spectral data of all synthesized diastereomers with that of reported for the natural product. Wittig-Horner reaction of -keto phosphonate derived from (S)-lactic acid and ring closing metathesis reaction were employed as key reactions in the total synthesis of synargentolide B 1 (scheme 3 and 4). Scheme 3: Total synthesis of possible diastereomers of synargentolide B (1a, 1b). Scheme 4: Total synthesis of possible diastereomers of synargentolide B (1c, 1d). [This work has been published: Prasad, K. R.; Gutala, P. J. Org. Chem. (in press)]. It was found that spectral data of 1a, 1b, 1c were not in agreement with that reported for synargentolide B 1. However spectral data of 1d was in complete agreement with the data reported for synargentolide B 1. Spectral data of 1d was also in complete agreement with the data reported for the natural product isolated by Pereda-Miranda, R. et al. Since the absolute stereochemistry of tetraacetate 2 is identical to the absolute stereochemistry of 1d, we wanted to confirm the integrity of the diol 1d by synthesizing the corresponding acetate 2 which was also a natural product isolated by Pereda-Miranda et al. 1H NMR data of the synthesized tetraacetate 2 was in agreement with that reported for the isolated tetraacetate, while discrepancies were observed in the 13C NMR spectral data. To clear the uncertainty, X-ray crystal structure analysis of the tetraacetate 2 was performed. It was comprehensively proved that the structure of synthesized tetraacetate 2 was indeed same as the putative structure proposed for the isolated tetraacetate by Pereda-Miranda et al. The crystal structure analysis also confirmed the absolute stereochemistry of the tetraacetate 2 and 1d (synargentolide B 1). (For structural formula pl refer the abstract pdf file)

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