Chemical Synthesis of the GHIJK Ring System and Further Experimental Support for the Originally Assigned Structure of Maitotoxin

Nicolaou, K. C.; Cole, Kevin P.; Frederick, Michael O.; Aversa, Robert J.; Denton, Ross M.

doi:10.1002/anie.200703742

Cited by 71 publications

(53 citation statements)

References 40 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The construction of this target molecule was based primarily on synthetic technologies previously developed in these laboratories and incorporating improvements reported from other groups. Specifically a Noyori reduction/Achmatowicz rearrangement-based tetrahydropyran synthesis,5,12,32 a hydroxy epoxide opening,13 a metathesis-based ring closure,10b–h,17,24 and a hydroxy dithioketal cyclization/methylation were employed 4b,9a–b,16,33. With this domain ( 7 ) of maitotoxin now synthesized, a set of six large domains (i.e.…”

Section: Resultsmentioning

confidence: 99%

“…With this domain ( 7 ) of maitotoxin now synthesized, a set of six large domains (i.e. 2–7 , Figure 1) of this neurotoxin have been completed 1,5–8. With appropriate modifications, the developed routes to these fragments can, in principle, deliver suitable fragments, whose coupling and further elaboration may lead to even larger domains of the natural product.…”

Section: Resultsmentioning

confidence: 99%

“…1) of this molecule and confirm its original stereochemical assignment3 through 13 C NMR comparison with the natural product. With this accomplishment, all the major domains of maitotoxin ( 1 ) have now been synthesized, including fragments 2 5, 3 6, 4 7, 5 8, 6 1 and 7 (present work) (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis of the WXYZA′ Domain of Maitotoxin

2010

View full text Add to dashboard Cite

A synthesis of the WXYZA′ domain (7) of the marine neurotoxin maitotoxin (1) is reported. The convergent synthetic strategy involves construction of key building blocks 11 and 12, their coupling, and the elaboration of the resulting ester (10) to the target molecule through a ringclosing metathesis and a hydroxy dithioketal cyclization as the key steps. For the construction of fragment 11, the Noyori reduction/Achmatowicz rearrangement and hydroxy epoxide opening technologies were applied [starting from furfuryl alcohol (13)], whereas for the synthesis of fragment 12, a carbohydrate-based approach was adopted [starting from 2-deoxy-D-ribose (14)]. The synthesized WXYZA′ domain (7) of maitotoxin (1) exhibited the expected 13 C NMR chemical shifts, supporting the originally assigned structure of the corresponding region of the natural product.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of the WXYZA′ Domain of Maitotoxin

2010

View full text Add to dashboard Cite

show abstract

“…Synthesis of the G-ring was planned from furfuryl alcohol 197 . 250 The ABCDE pentacyclic system was disconnected into smaller fragments which were designed from appropriate furan precursors. Accordingly, the ABCDE ring system could be built upon C ring disconnection through a β-alkyl Suzuki coupling and an acetal formation/methylation of the AB endocyclic ketene acetal phosphate 221 with vinyl ether 222 as the required synthons.…”

Section: Introductionmentioning

confidence: 99%

Achmatowicz reaction and its application in the syntheses of bioactive molecules

Ghosh

Brindisi

2016

RSC Adv.

View full text Add to dashboard Cite

Substituted pyranones and tetrahydropyrans are structural subunits of many bioactive natural products. Considerable efforts are devoted toward the chemical synthesis of these natural products due to their therapeutic potential as well as low natural abundance. These embedded pyranones and tetrahydropyran structural motifs have been the subject of synthetic interest over the years. While there are methods available for the syntheses of these subunits, there are issues related to regio and stereochemical outcomes, as well as versatility and compatibility of reaction conditions and functional group tolerance. The Achmatowicz reaction, an oxidative ring enlargement of furyl alcohol, was developed in the 1970s. The reaction provides a unique entry to a variety of pyranone derivatives from functionalized furanyl alcohols. These pyranones provide convenient access to substituted tetrahydropyran derivatives. This review outlines general approaches to the synthesis of tetrahydropyrans, covering general mechanistic aspects of the Achmatowicz reaction or rearrangement with an overview of the reagents utilized for the Achmatowicz reaction. The review then focuses on the synthesis of functionalized tetrahydropyrans and pyranones and their applications in the synthesis of natural products and medicinal agents.

show abstract

“…With compound 11 in hand, the trisubstituted alkene was converted to the a,b-unsaturated methyl ester through the standard oxidative cleavage/olefination protocol (Scheme 2). Ring expansion of the furan ring through the Achmatowicz reaction [15] followed by methylation of the resultant lactol afforded compound 13, which is intended to be converted to 14 and 15 by olefination. Surprisingly, the ketone moiety of compound 13 was found to be unreactive under a variety of conventional olefination conditions probably due to its steric hindrance.…”

mentioning

confidence: 99%

A Biomimetic Synthesis of (±)‐Basiliolide B

et al. 2014

View full text Add to dashboard Cite

A highly diastereoselective and practical biomimetic total synthesis of (AE)-basiliolide B has been achieved through the study of the two proposed biosynthetic pathways (Omethylation and O-acylation) for the unprecedented 7methoxy-4,5-dihydro-3H-oxepin-2-one (C ring). The synthesis featured a cyclopropanation/ring opening strategy for establishing the stereogenic centers at C8 and C9, a biomimetic 2pyrone Diels-Alder cycloaddition for the synthesis of the ABD ring system, and finally a highly efficient biomimetic intramolecular O-acylation for the C ring formation. This result provides an important perspective on the biosynthetic origin of the unprecedented 7-membered acyl ketene acetal moiety of the C ring.

show abstract

Chemical Synthesis of the GHIJK Ring System and Further Experimental Support for the Originally Assigned Structure of Maitotoxin

Cited by 71 publications

References 40 publications

Synthesis of the WXYZA′ Domain of Maitotoxin

Synthesis of the WXYZA′ Domain of Maitotoxin

Achmatowicz reaction and its application in the syntheses of bioactive molecules

A Biomimetic Synthesis of (±)‐Basiliolide B

Contact Info

Product

Resources

About