Enantioselective total synthesis of (+)-12,13-epoxytrichothec-9-ene and its antipode

Hua, Duy H.; Venkataraman, S.; Chan, R. Y. K.; Paukstelis, Joseph V.

doi:10.1021/ja00222a036

Cited by 50 publications

(27 citation statements)

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“…Perhaps more critically, methods to efficiently and reliably prepare the requisite functionalized cyclopentenones ( 14 ) are lacking. Indeed, while cyclopentenones can be prepared by a number of different pathways, including metalation chemistry,6 Michael additions/reoxidations,7 metal cyclizations/Conia ene chemistry,8 and Nazarov cyclizations,9 general, mild, and step‐economic processes have not been demonstrated for many variants of the types desired as broadly defined by R within 14 . Herein, we detail a simple, two‐step solution capable of affording structurally diverse cyclopentenones.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Applications of Hajos–Parrish Ketone Isomers

Eagan

Hori

et al. 2015

Angewandte Chemie

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Numerous natural products possess ring systems and functionality for which Hajos–Parrish ketone isomers with a transposed methyl group (termed “iso‐Hajos–Parrish ketones”) would be of value. However, such building blocks have not been exploited to the same degree as the more typical Hajos–Parrish hydrindane. An efficient three‐step synthesis of such materials was fueled by a simple method for the rapid preparation of highly functionalized cyclopentenones, several of which are new chemical entities that would be challenging to access through other approaches. Furthermore, one iso‐Hajos–Parrish ketone was converted into two distinct natural product analogues and one natural product. As one indication of the value of these new building blocks, that latter target was obtained in 10 steps, having previously been accessed in 18 steps using the Hajos–Parrish ketone.

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Section: Methodsmentioning

confidence: 99%

Synthesis and Applications of Hajos–Parrish Ketone Isomers

Eagan

Hori

et al. 2015

Angewandte Chemie

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“…In 2010, Zhang and Danishefsky disclosed the first total synthesis of (±)‐aplykurodinone‐1 [8] . As shown in Scheme 1, the synthesis commenced with a Diels‐Alder cycloaddition reaction between metallo‐enolate derived from siloxy diene 7 [9] and 2‐(methoxycarbonyl)‐3‐methyl‐2‐cyclopentenone 8 [10] to afford 9 in 73% yield. The three following steps involved regioselective protection of the enone as a thioacetal, followed by reduction of the ketone carbonyl and formation of the MOM ether to give 11 , which was then converted to 12 after the reduction of the ester and hydrolysis of the thioacetal.…”

Section: The Synthetic Approaches Toward Aplykurodinone‐1mentioning

confidence: 99%

Synthetic Approaches of Aplykurodinone‐1: A Minireview

Xun

2022

Asian J Org Chem

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Aplykurodinone‐1, a marine steroid with intriguing molecular architecture and promising biological activities, has captured the attention of many synthetic chemists. In this paper we have overviewed the synthetic approaches of aplykurodinone‐1 to date, with a focus on the novel strategies utilized to improve the synthetic efficiency. This review summarizes the contribution of different research groups in the total or formal synthesis of aplykurodinone‐1 in either racemic or enantiomeric form.

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“…Overman and Mislow-Evans rearrangements furnishing allylic amines and sulfoxides, respectively, have already been reported with cyclic allylic alcohol substrates. [25] We decided to pursue a Claisen rearrangement. At first, the Johnson protocol, that is, treatment with triethyl orthoacetate in the presence of propionic acid, was attempted; however, unsatisfying results were achieved.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

Improved Synthesis of Cyclic Tertiary Allylic Alcohols by Asymmetric 1,2‐Addition of AlMe₃ to Enones

Kolb

Zuo

Siewert

et al. 2013

Chemistry A European J

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The development of an improved protocol for the enantioselective Rh(I) /binap-catalysed 1,2-addition of AlMe3 to cyclic enones is reported. (31)P NMR analysis of the reaction revealed that the catalyst in its resting state is a chloride-bridged dimer. This insight led to the use of AgBF4 as an additive for in situ activation of the dimeric precatalyst. Thus, the catalyst loading can now be reduced to only 1 mol% with respect to rhodium. Various 5-7-membered cyclic enones can be transformed into tertiary allylic alcohols with excellent levels of enantioselectivity and high yields. The obtained products are versatile synthetic building blocks, shown by a highly enantioselective formal total synthesis of the pheromone (-)-frontalin as well as formation of a bicyclic lactone that has the core structure of the natural flavour component "wine lactone".

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Enantioselective total synthesis of (+)-12,13-epoxytrichothec-9-ene and its antipode

Cited by 50 publications

References 0 publications

Synthesis and Applications of Hajos–Parrish Ketone Isomers

Synthesis and Applications of Hajos–Parrish Ketone Isomers

Synthetic Approaches of Aplykurodinone‐1: A Minireview

Improved Synthesis of Cyclic Tertiary Allylic Alcohols by Asymmetric 1,2‐Addition of AlMe₃ to Enones

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Enantioselective total synthesis of (+)-12,13-epoxytrichothec-9-ene and its antipode

Cited by 50 publications

References 0 publications

Synthesis and Applications of Hajos–Parrish Ketone Isomers

Synthesis and Applications of Hajos–Parrish Ketone Isomers

Synthetic Approaches of Aplykurodinone‐1: A Minireview

Improved Synthesis of Cyclic Tertiary Allylic Alcohols by Asymmetric 1,2‐Addition of AlMe3 to Enones

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Improved Synthesis of Cyclic Tertiary Allylic Alcohols by Asymmetric 1,2‐Addition of AlMe₃ to Enones