Catalytic Asymmetric Total Synthesis of <i>ent</i>‐Hyperforin

Shimizu, Y.; Shi, Shiliang; Usuda, Hiroyuki; Kanai, Motomu; Shibasaki, Masakatsu

doi:10.1002/ange.200906678

Cited by 30 publications

(19 citation statements)

References 41 publications

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“…2b). 11 The quaternary stereocenter of cycloadduct 9 subsequently played a decisive role in evolving the two additional quaternary stereocenters of ent -hyperforin. Catalytic enantioselective Diels–Alder reactions that form quaternary stereocenters have been orchestrated also in various intramolecular fashions, including macrobicyclization 12 and transannular processes.…”

Section: Cycloaddition Reactionsmentioning

confidence: 99%

“…b , An iron-bisoxazoline catalyzed bimolecular Diels–Alder reaction forms product 9 whose quaternary stereocenter subsequently controlled the elaboration of the two additional quaternary stereocenters of ent -hyperforin ( 10 ). 11 TIPS, triisopropylsilyl; Et, ethyl; MS, molecular sieves. c , Oxazaborolidinium-catalyzed intramolecular Diels–Alder reaction to form the 11-membered ring and quaternary stereocenter of palominol ( 14 ).…”

Section: Figurementioning

confidence: 99%

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Catalytic enantioselective synthesis of quaternary carbon stereocentres

Quasdorf

Overman

2014

Nature

850

341

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Preface Quaternary carbon stereocenters–carbon atoms to which four distinct carbon substituents are attached–are common features of molecules found in nature. However, prior to recent advances in chemical catalysis, there were few methods available for constructing single stereoisomers of this important structural motif. Here we discuss the many catalytic enantioselective reactions developed during the past decade for synthesizing organic molecules containing such carbon atoms. This progress now makes it possible to selectively incorporate quaternary stereocenters in many high-value organic molecules for use in medicine, agriculture, and other areas.

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Section: Cycloaddition Reactionsmentioning

confidence: 99%

Section: Figurementioning

confidence: 99%

Catalytic enantioselective synthesis of quaternary carbon stereocentres

Quasdorf

Overman

2014

Nature

850

341

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“…[216] This approach stems from a catalytic asymmetric Diels–Alder reaction [217] between dienophile 231 and diene 232 promoted by an Fe III complex with PyBOX ligand 233 (Scheme 37). Claisen rearrangement [92] of allyl enol ether 235 installed the C1 quaternary center of 236 .…”

Section: Neurotrophic Natural Productsmentioning

confidence: 99%

Neurotrophic Natural Products: Chemistry and Biology

2013

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Neurodegenerative diseases and spinal cord injury affect approximately 50 million people worldwide, bringing the total healthcare cost to over 600 billion dollars per year. Nervous system growth factors, that is, neurotrophins, are a potential solution to these disorders, since they could promote nerve regeneration. An average of 500 publications per year attests to the significance of neurotrophins in biomedical sciences and underlines their potential for therapeutic applications. Nonetheless, the poor pharmacokinetic profile of neurotrophins severely restricts their clinical use. On the other hand, small molecules that modulate neurotrophic activity offer a promising therapeutic approach against neurological disorders. Nature has provided an impressive array of natural products that have potent neurotrophic activities. This Review highlights the current synthetic strategies toward these compounds and summarizes their ability to induce neuronal growth and rehabilitation. It is anticipated that neurotrophic natural products could be used not only as starting points in drug design but also as tools to study the next frontier in biomedical sciences: the brain activity map project.

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“…High enantioselectivity (up to 92% ee) was obtained using a catalyst generated from FeBr 3 and (R,R)-aryl-pybox 56 (Scheme 43). Application of this methodology to the enantioselective synthesis of hyperforin, garsubellin A or enthyperforin was accomplished by the same authors [91,92].…”

Section: Scheme 42mentioning

confidence: 99%

Recent advances in the iron-catalyzed cycloaddition reactions

Wang

Wan

2012

Chin. Sci. Bull.

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The rapid generation of molecular in a relatively easy manner has made the cycloaddition reaction a powerful tool in the synthesis of different membered ring compounds. Clearly, iron catalysts are becoming a much more interesting and viable choice for this purpose. In this review, a number of promising results in the iron catalyzed cycloaddition reactions in the last decades were summarized. Special attention has been paid to the asymmetric cycloaddition reactions. cycloaddition, iron catalyst, asymmetric Citation:Wang C X, Wan B S. Recent advances in the iron-catalyzed cycloaddition reactions. Chin Sci Bull, 2012, 57: 23382351, doi: 10.1007/s11434-012-5141-z Cycloaddition reaction, which can construct several bonds simultaneously in a single step, is one of the most powerful strategies for the synthesis of cyclic compounds from various unsaturated substrates such as alkynes, alkenes, allenes, nitriles, aldehydes, ketones, imines, etc. Three-, four-, five-, six-or seven-membered rings are obtained through these transformations. The high atom-efficiency, as well as the good tolerance of different functional groups, continues to draw many chemists' attention to this field. In particular, great efforts have been devoted to the development of novel and efficient catalytic systems. However, harsh reaction conditions are often required including heat, light, high pressure or sonication, and the lack of chemo-and/or regioselectivity is also an important problem. Over the past decades, the use of transition metal catalysts has contributed significantly to the development of the cycloaddition reactions and good selectivities were obtained [1]. Among all the available transition metals, iron is generally regarded as one of the most inexpensive, abundant, benign and relatively non-toxic metals [2]. Many transformations have been effectively promoted by iron catalysts, and excellent reviews on the iron-catalyzed reactions are available [3][4][5][6][7][8][9][10][11][12][13][14][15]. Bolm and co-workers [3] summarized the most important transformations with the aid of iron catalysts in 2004, including addition, substitution, cycloaddition, reduction and other reactions. At a later time, they also reviewed the oxidative C-C coupling reactions [4] and the development of carbon-heteroatom and heteroatom-heteroatom bond formation under iron catalysts [5]. The uses of FeCl 3 as catalyst in organic synthesis were covered by Padrón [6] and Bolm [4], and the cross coupling reactions were discussed in detail by Fürstner [7,8]. Recently, direct C-H transformation via iron catalysis was summarized by Shi and co-workers [9]. Applications of iron catalysts on other reactions were also summarized by Bauer [10] However, despite the aforementioned contributions, reviews mainly focus on the iron-catalyzed cycloaddition reactions are rather rare [15]. In this review, we will point out recent advances in this field, most contributions going from 2004 to Nov. 2011. Although every effort has been made to avoid repetition, some overlap with the ...

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Catalytic Asymmetric Total Synthesis of ent‐Hyperforin

Cited by 30 publications

References 41 publications

Catalytic enantioselective synthesis of quaternary carbon stereocentres

Catalytic enantioselective synthesis of quaternary carbon stereocentres

Neurotrophic Natural Products: Chemistry and Biology

Recent advances in the iron-catalyzed cycloaddition reactions

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