The [2,3]‐Wittig Rearrangement

Isobe, Mitsuaki; Ploysuk, Chatchawan

doi:10.1002/9781118939901.ch17

Cited by 7 publications

(13 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Application of the [2,3]-Wittig rearrangement to the synthesis of hindered homoallylic alcohol fragments in a variety of natural products and pharmaceutical agents stands as a testament to its utility. 4 , 5 , 23 − 27 Furthermore, this intramolecular O–C allyl transfer is representative of the broader class of anionic sigmatropic rearrangements. 22 While significant advances have been made toward enantioselective catalysis of rearrangements with related ylides, 5 , 6 , 28 − 32 development of a general, catalytic, enantioselective [2,3]-Wittig rearrangement has lagged.…”

Section: Introductionmentioning

confidence: 98%

Synergistic Ion-Binding Catalysis Demonstrated via an Enantioselective, Catalytic [2,3]-Wittig Rearrangement

2016

View full text Add to dashboard Cite

Sigmatropic rearrangements number among the most powerful complexity-building transformations in organic synthesis but have remained largely insensitive to enantioselective catalysis due to the diffuse nature of their transition structures. Here, we describe a synergistic ion-binding strategy for asymmetric catalysis of anionic sigmatropic rearrangements. This approach is demonstrated with the enantioselective [2,3]-Wittig rearrangement of α-allyloxy carbonyl compounds to afford highly enantioenriched homoallylic alcohol products. Chiral thiourea catalysts are shown to engage reactive anions and their countercations through a cooperative set of attractive, noncovalent interactions. Catalyst structure–reactivity–selectivity relationship studies and computational analyses provide insight into catalyst–substrate interactions responsible for enantioinduction and allude to the potential generality of this catalytic strategy.

show abstract

Section: Introductionmentioning

confidence: 98%

Synergistic Ion-Binding Catalysis Demonstrated via an Enantioselective, Catalytic [2,3]-Wittig Rearrangement

2016

View full text Add to dashboard Cite

show abstract

“…Recently we have published a systematic study of [2,3]-Wittig rearrangements of dihydropyran-propargyl ethers, as well as a review article . In this article we reported that, in the cases where stabilization of the precursor was possible through the formation of a five membered-ring chelate of lithium coordinating with the ether oxygen atom, a higher energy to overcome the transition state of the concerted reaction was sometimes required in a cyclic system.…”

Section: Discussionmentioning

confidence: 77%

Synthesis of Rings DEF of Solanoeclepin A

Chuang

Isobe

2017

J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

An improved synthesis of rings DEF of solanoeclepin A has been achieved from ent-Hajos Parrish ketone. A key tricyclo[5.3.2.0]decene intermediate having an additional vinyl group as a precursor of a hydroxyl functionality was synthesized, in which the key steps included (i) a [2,3]-Wittig rearrangement to provide trans-hydroindene with C11(R)-configuration, (ii) the introduction of a vinyl group as a masked OH at C6, (iii) an oxymercurative aldol to synthesize the tricyclo[5.3.2.0]decene moiety, (iv) an oxidative C-C bond cleavage to yield an aldehyde and an unsaturated methyl ketone, and (v) a radical cyclization for the cyclobutane ring formation to provide the tricyclo[5.2.1.0]decene compound.

show abstract

“…Among the several approaches that have been employed for their synthesis [37][38][39][40][41][42][43][44][45], the [2,3]-Wittig rearrangement of propargylic ethers represents an efficient way to assemble them [46,47]. The major limitation of this versatile bond reorganization process, which has many other applications in organic synthesis, is mainly correlated to the use of strong bases and very low temperatures together with the laborious, complicated, and expensive procedures required [48][49][50].…”

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical DFT Investigations in the [2,3]-Wittig-Type Rearrangement of Propargyl/Allyl-Oxy-Pyrazolones

et al. 2021

View full text Add to dashboard Cite

Here we report the synthesis of interesting 3-alkyl-4-hydroxy-1-aryl-4-(propa-1,2-dienyl)1H-pyrazol-5(4H)-ones and 9-alkyl-7-aryl-1-oxa-7,8-diazaspiro[4.4]nona-3,8-dien-6-ones, starting from 1,2-diaza-1,3-dienes (DDs) and propargyl alcohol. The reaction proceeds through a sequence Michael-type nucleophilic attack/cyclization/[2,3]-Wittig rearrangement. In the same way, the reaction between the aforementioned DDs and allyl alcohol furnished 4-allyl-4-hydroxy-3-alkyl-1-aryl-1H-pyrazol-5(4H)-ones. A DFT study was also carried out, in order to have decisive clarifications about the mechanism.

show abstract

The [2,3]‐Wittig Rearrangement

Cited by 7 publications

References 47 publications

Synergistic Ion-Binding Catalysis Demonstrated via an Enantioselective, Catalytic [2,3]-Wittig Rearrangement

Synergistic Ion-Binding Catalysis Demonstrated via an Enantioselective, Catalytic [2,3]-Wittig Rearrangement

Synthesis of Rings DEF of Solanoeclepin A

Experimental and Theoretical DFT Investigations in the [2,3]-Wittig-Type Rearrangement of Propargyl/Allyl-Oxy-Pyrazolones

Contact Info

Product

Resources

About