Total Synthesis of (&amp;#xB1;)-Euryfuran Through Ti(III) Catalyzed Radical Cyclization

Rosales, Antonio; López-Sánchez, Cristóbal; Álvarez-Corral, Míriam; Muooz-Dorado, Manuel; Rodrı́guez-Garcı́a, Ignacio

doi:10.2174/157017807782795457

Cited by 14 publications

(9 citation statements)

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“…As a continuation of our research on the synthesis of marine natural bioactive compounds [18,[21][22][23], we have developed a new concise route for the synthesis of tetracyclic meroterpenoids. In this new synthetic route, aureol (1) is the key intermediate from which other tetracyclic meroterpenoids, such as 2, 3 and 4, can be easily synthesized by simple functional modification of its aromatic ring.…”

Section: Resultsmentioning

confidence: 99%

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A Concise Route for the Synthesis of Tetracyclic Meroterpenoids: (±)-Aureol Preparation and Mechanistic Interpretation

et al. 2020

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A new concise general methodology for the synthesis of different tetracyclic meroterpenoids is reported: (±)‑aureol (1), the key intermediate of this general route. The synthesis of (±)‑aureol (1) was achieved in seven steps (28% overall yield) from (±)‑albicanol. The key steps of this route include a C–C bond-forming reaction between (±)‑albicanal and a lithiated arene unit and a rearrangement involving 1,2‑hydride and 1,2-methyl shifts promoted by BF3•Et2O as activator and water as initiator.

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Section: Resultsmentioning

confidence: 99%

“…CDCl 3 was always used as NMR solvent. (±)-Albicanol was prepared from commercial farnesol according to a known procedure [22,24]. Copies of 1 H and 13 C NMR spectra of relevant known compounds are provided in Supplementary Materials.…”

Section: General Methodsmentioning

confidence: 99%

A Concise Route for the Synthesis of Tetracyclic Meroterpenoids: (±)-Aureol Preparation and Mechanistic Interpretation

et al. 2020

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“…Due to the fascinating chemical structures and biological properties of marine meroterpenoids, our research group and the group led by Prof. Oltra [ 12 , 30 , 31 , 32 , 33 , 34 , 35 , 36 ] began to develop methodologies for the total synthesis of this group of natural marine compounds. Along with Gansäuer group [ 37 , 38 ], we have contributed to the acquisition of marine meroterpenoids through the diastereoselective radical cyclization of epoxypolyenes catalyzed by Cp 2 TiCl as a new green monoelectronic transfer complex [ 39 , 40 ].…”

Section: Synthesis Of the Tetracyclic Alkenes 12a–dmentioning

confidence: 99%

Unifying the Synthesis of a Whole Family of Marine Meroterpenoids through a Biosynthetically Inspired Sequence of 1,2-Hydride and Methyl Shifts as Key Step

2023

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Marine meroterpenoids have attracted a great deal of attention from synthetic research groups due to their attractive and varied biological activities and their unique and diverse structures. In most cases, however, further biological studies have been severely limited mainly to the scarcity of natural supply and because almost none of the reported syntheses methods has enabled unified access for a large number of marine meroterpenoids with aureane and avarane skeletons. Based on our previous publications and the study of recent manuscripts on marine meroterpenoids, we have conceived a unified strategy for these fascinating marine compounds with aureane or avarane skeletons using available drimane compounds as starting materials. The key step is a biosynthetic sequence of 1,2-hydride and methyl shifts. This strategy is of great synthetic value to access marine meroterpenoids through easy chemical synthetic procedures. Finally, several retrosynthetic proposals are made for the future synthesis of several members of this class of meroterpenoids, focused on consolidating these 1,2-rearrangements as a versatile and unified strategy that could be widely used in the preparation of these marine meroterpenoids.

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“…The modulation of the last step of the cyclization process (termination) is crucial for the synthesis of many natural terpenes. The presence of an allylic acetate ( 241 , 247 ) (Scheme ) or an aromatic ring ( 238 , 244 , 252 ) prepares the system for the completion of the carbon skeleton, thus allowing the synthesis of umbrosone ( 240 ), the marine furanoditerpenoid 243 , aureol ( 246 ), eurifuran ( 250 ), cyclozonarone ( 251 ), ambrox ( 249 ), or pupehedione ( 254 ) …”

Section: Applications Of Cp2ticlmentioning

confidence: 99%

“…22,55 The modulation of the last step of the cyclization process (termination) is crucial for the synthesis of many natural terpenes. The presence of an allylic acetate (241, 247) (Scheme 29) or an aromatic ring (238, 244, 252) prepares the system for the completion of the carbon skeleton, thus allowing the synthesis of umbrosone (240), 67 the marine furanoditerpenoid 243, 68 aureol (246), 69 eurifuran (250), 70 cyclozonarone (251), 71 ambrox (249), 72 or pupehedione (254). 73 Cp 2 TiCl finds another interesting application in the deuteration of organic compounds 74 and the synthesis of β-deuterated alcohols for their use as internal standards in food analysis.…”

Section: ■ Applications Of Cp 2 Ticlmentioning

confidence: 99%

The Proven Versatility of Cp₂TiCl

et al. 2020

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In the last two decades, titanocene monochloride has been postulated as a monoelectronic transfer reagent capable of catalyzing an important variety of chemical transformations. In this Perspective, our contributions to this growing field of research are summarized and analyzed. Especially known have been our contributions in C–C bond formation reactions, hydrogen-atom transfer from water to radicals, and isomerization reactions, as well as the development of a catalytic cycle that has subsequently allowed the preparation of a great variety of natural terpenes. It is also worth mentioning our contribution in the postulation of this single-electron transfer agent (SET) as a new green catalyst with a broad range of applications in organic and organometallic chemistry. The most significant catalytic processes developed by other research groups are also briefly described, with special emphasis on the reaction mechanisms involved. Finally, a reflection is made on the future trends in the research of this SET, aimed at consolidating this chemical as a new green reagent that will be widely used in fine chemistry, green chemistry, and industrial chemical processes.

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Total Synthesis of (±)-Euryfuran Through Ti(III) Catalyzed Radical Cyclization

Cited by 14 publications

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A Concise Route for the Synthesis of Tetracyclic Meroterpenoids: (±)-Aureol Preparation and Mechanistic Interpretation

A Concise Route for the Synthesis of Tetracyclic Meroterpenoids: (±)-Aureol Preparation and Mechanistic Interpretation

Unifying the Synthesis of a Whole Family of Marine Meroterpenoids through a Biosynthetically Inspired Sequence of 1,2-Hydride and Methyl Shifts as Key Step

The Proven Versatility of Cp₂TiCl

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Total Synthesis of (&#xB1;)-Euryfuran Through Ti(III) Catalyzed Radical Cyclization

Cited by 14 publications

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A Concise Route for the Synthesis of Tetracyclic Meroterpenoids: (±)-Aureol Preparation and Mechanistic Interpretation

A Concise Route for the Synthesis of Tetracyclic Meroterpenoids: (±)-Aureol Preparation and Mechanistic Interpretation

Unifying the Synthesis of a Whole Family of Marine Meroterpenoids through a Biosynthetically Inspired Sequence of 1,2-Hydride and Methyl Shifts as Key Step

The Proven Versatility of Cp2TiCl

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Total Synthesis of (±)-Euryfuran Through Ti(III) Catalyzed Radical Cyclization

The Proven Versatility of Cp₂TiCl