Bioinspired Total Synthesis of Bolivianine: A Diels– Alder/Intramolecular Hetero-Diels–Alder Cascade Approach

Yuan, Changchun; Du, Biao; Yang, Li; Liu, Bo

doi:10.1021/ja4040335

Cited by 96 publications

(30 citation statements)

References 53 publications

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“…As an example, as many as four new stereocenters can be prepared in a single step using the DA reaction (Scheme ). There are an enormous number of reports in which the DA reaction was applied for the synthesis of new materials and natural products . Quite recently, cyclopentadienes with Raman and electrochemically active tags were patterned covalently onto graphene surfaces using force‐accelerated DA reactions …”

Section: Introductionmentioning

confidence: 99%

A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

Cui

Liu

2014

J of Physical Organic Chem

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The Diels-Alder (DA) reaction is one of the most important reactions in organic chemistry. The controversy surrounding this reaction as to whether it follows a concerted or stepwise mechanism has existed for a long time. The reaction of 1,3-butadiene and ethylene is the paradigmatic example of the DA reaction. We have reinvestigated the mechanism of this reaction using density functional theory. The theoretical study considered all types of possible pathways for the reaction of 1,3-butadiene and ethylene using six functionals at different rungs of Jacob's ladder. Therefore, a complete picture is given for a thorough understanding of the iconic DA reaction, and a new stationary point during the reaction processes has been reported for the first time. The calculated results indicated that three functionals, ωB97X-D, M06-2X, and B2-PLYP, of the fourth and fifth rungs of Jacob's ladder performed well in the investigation of the mechanism of this reaction and that the reliable basis set should be larger than 6-311+G(2d,p). The cis-1,3-butadiene more easily reacted with ethylene compared with 1,3-butadiene in the trans conformation. The concerted mechanism was found to be energetically favorable, whose energy barrier is around 10 kcal/mol lower than that of the stepwise mechanism. Two investigated solvents, toluene and CH 3 CN, had little impact on this simple DA reaction.

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Section: Introductionmentioning

confidence: 99%

A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

Cui

Liu

2014

J of Physical Organic Chem

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“…[35] The DA reaction of onoseriolide (46) with b-E-ocimene (47) led to the intermediate 48 which concomitantly underwent an intramolecular oxa-Diels-Alder reaction between the a,b-unsaturated aldehyde moiety of onoseriolide and the remaining double bond of 47 (Scheme 8). [36] By means of this elegant and ambitious DA/IMHDA cascade, the EFG tricycle of bolivianine (49) was formed in one step.…”

Section: Methodsmentioning

confidence: 99%

The Asymmetric Hetero‐Diels–Alder Reaction in the Syntheses of Biologically Relevant Compounds

Eschenbrenner‐Lux¹,

Kumar²,

Waldmann³

2014

Angew Chem Int Ed

213

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The hetero-Diels-Alder reaction is one of the most powerful transformations in the chemistry toolbox for the synthesis of aza- and oxa-heterocycles embodying multiple stereogenic centers. However, as compared to other cycloadditions, in particular the dipolar cycloadditions and the Diels-Alder reaction, the hetero-Diels-Alder reaction has been much less explored and exploited in organic synthesis. Nevertheless, this powerful transformation has opened up efficient and creative routes to biologically relevant small molecules and different natural products which contain six-membered oxygen or nitrogen ring systems. Recent developments in this field, in particular in the establishment of enantioselectively catalyzed hetero-Diels-Alder cycloadditions steered by a plethora of different catalysts and the application of the resulting small molecules in chemical biology and medicinal chemistry research, are highlighted in this Minireview.

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“…Herein we highlight Liu’s successful execution of this idea resulting in a highly concise route to 68 and 69 from verbenone. 99,100 …”

Section: Syntheses From the 21st Centurymentioning

confidence: 99%

Navigating the Chiral Pool in the Total Synthesis of Complex Terpene Natural Products

et al. 2017

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The pool of abundant chiral terpene building blocks (i.e. “chiral pool terpenes”) has long served as a starting point for the chemical synthesis of complex natural products, including many terpenes themselves. As inexpensive and versatile starting materials, such compounds continue to influence modern synthetic chemistry. This review highlights 21st century terpene total syntheses which themselves use small, terpene-derived materials as building blocks. An outlook to the future of research in this area is highlighted as well.

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Bioinspired Total Synthesis of Bolivianine: A Diels– Alder/Intramolecular Hetero-Diels–Alder Cascade Approach

Cited by 96 publications

References 53 publications

A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

The Asymmetric Hetero‐Diels–Alder Reaction in the Syntheses of Biologically Relevant Compounds

Navigating the Chiral Pool in the Total Synthesis of Complex Terpene Natural Products

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