Electrophile‐Induced Ether Transfer: Stereoselective Synthesis of 2,4,6‐Trisubstituted Tetrahydropyrans

Kartika, Rendy; Taylor, Richard E.

doi:10.1002/anie.200702018

Cited by 31 publications

(12 citation statements)

References 25 publications

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“…[4d] For preparation of the tertiary alcohol, we envisioned the installation of the 1,3- syn diol through utilization of an electrophilic-induced ether transfer methodology recently developed in our labs. [5] The alkene required for the subsequent RCM step provided us with an opportunity to explore a unique ether transfer substrate which contains potentially competing 1,1-disubstituted and terminal alkenes.…”

mentioning

confidence: 99%

Total Synthesis and Structural Reassignment of Lyngbyaloside C Highlighted by Intermolecular Ketene Esterification

Chang

Stefan

Taylor

2015

Chemistry A European J

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Lyngbyaloside C, a classic macrolide, isolated from Lyngbya bouilloni, has shown moderate anticancer activity against several cancer cell lines. Here, we report the first total synthesis and stereochemical configuration reassignment of lyngbyaloside C. The synthesis highlights a one-pot intermolecular ketene esterification reaction to form the crucial tertiary ester and tetrahydropyran. In addition, a novel and concise synthetic pathway towards the 1,3-syn secondary, tertiary diol fragment is described using a regio- and stereospecific electrophilic ether transfer reaction.

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confidence: 99%

Total Synthesis and Structural Reassignment of Lyngbyaloside C Highlighted by Intermolecular Ketene Esterification

Chang

Stefan

Taylor

2015

Chemistry A European J

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“…In fact, after the activation of the double bond with a electrophilic reagent, an oxygen from an ether can react as a nucleophile generating a oxonium ion intermediate that can be trapped by a variety of nucleophiles. This method was developed by the Taylor group 42 and has been applied successfully to the synthesis of 2,4,6trisubstituted tetrahydropyrans 43 and 2,6-disubstituted 3,4-dihydropyrans. 44 The main idea and applications are illustrated in Scheme 19.…”

Section: Scheme 18 Organocatalyzed Carbon Dioxide Fixationmentioning

confidence: 99%

Synthesis of 1,3-Diols by O-Nucleophile Additions to Activated Alkenes

Gamba‐Sánchez

Prunet

2018

Synthesis

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The diastereoselective synthesis of 1,3-diols by addition of oxygen nucleophiles to activated alkenes is presented. This review focuses on homoallylic alcohol substrates that react with a relay compound to form an intermediate oxygen nucleophile, which in turn will lead to a protected 1,3-diol by intramolecular addition to the olefin moiety.1 Introduction2 Base Catalysis3 Organocatalysis4 Activation with Non-Metallic Electrophiles5 Activation with Transition Metal Derivatives6 Conclusions

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“…In the total synthesis of the diarylheptanoid diospongin B, Hall and Rybak 50 used the silyl enol ether derived from acetophenone as the nucleophile to axially attack the in situ generated pyran oxocarbenium ion to form at a late stage the 2,6-trans-THP 2-2v with a satisfactory yield and diastereoselectivity. Taylor and co-workers 39 developed the stereoselective synthesis of 2,6-trans-THPs by AlCl 3 -promoted reactions of pyran sulfones (sulfone as a leaving group) with allylsilanes (2-2o) (Scheme 4), silyl enol ethers, and vinylogous silyl ketene acetals (2-2w) (Scheme 5), while H. M. R. Hoffmann et al 28 demonstrated that the protocol of TMSOTf-mediated Hosomi-Sakurai allylation of a pyran oxocarbenium ion could be applicable to the Mukaiyama aldol reaction with sterically demanding silyl ketene acetal 2-1x. In 2009, Crimmins et al 51 reported an elegant application of the Mukaiyama aldol reaction of a pyran oxocarbenium ion for the highly diastereoselective synthesis of 2,6trans-THP 2-2y in the total synthesis of psymberin (irciniastatin A).…”

Section: Syn Thesismentioning

confidence: 99%

Synthetic Approaches to 2,6-trans-Tetrahydropyrans

Tong

2017

Synthesis

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Being different from 2,6-cis-tetrahydropyrans (2,6-cis-THPs), the corresponding 2,6-trans-THPs are thermodynamically less stable and more challenging to construct. The fact that there are many natural products and/or bioactive molecules containing this 2,6-trans-THP subunit has led to the development of many efficient synthetic approaches to access 2,6-trans-THPs. This review summarizes various synthetic methods reported for this structural motif and/or related applications in the total synthesis of natural products.1 Introduction2 Nucleophilic Addition to an Oxocarbenium Ion (Strategy A)3 Intramolecular Oxa-Michael Addition (Strategy B)4 Intermolecular Michael Addition to Dihydropyranones (Strategy A)5 The Heck–Matsuda (Strategy A) Reaction and Oxa-Heck Cyclization (Strategy B)6 Intramolecular SN2 Substitution and Epoxide Opening (Strategy B)7 Miscellaneous Methods8 Conclusion and Outlook

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Electrophile‐Induced Ether Transfer: Stereoselective Synthesis of 2,4,6‐Trisubstituted Tetrahydropyrans

Cited by 31 publications

References 25 publications

Total Synthesis and Structural Reassignment of Lyngbyaloside C Highlighted by Intermolecular Ketene Esterification

Total Synthesis and Structural Reassignment of Lyngbyaloside C Highlighted by Intermolecular Ketene Esterification

Synthesis of 1,3-Diols by O-Nucleophile Additions to Activated Alkenes

Synthetic Approaches to 2,6-trans-Tetrahydropyrans

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