Regio- and stereoselective synthesis of (+)-6-ketoeuryfuran, (+)-6-ketowinterin, and (−)-7-ketoeuryfuran from accessible labdane diterpenoids (+)-larixol and (−)-sclareol

Vlad, P. F.; Ciocârlan, Alexandru; Edu, Carolina; Aricu, Aculina; Biriiac, Andrei; Coltsa, M. N.; D’Ambrosio, Michele; Deleanu, Călin; Nicolescu, Alina; Shova, Sergiu; Vornicu, Nicoleta; Groot, Aede de

doi:10.1016/j.tet.2012.10.096

Cited by 17 publications

(13 citation statements)

References 37 publications

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“…[6,15] Surprisingly, when (À)-2 was exposed to UV light (365 nm), (+ +)-1 was not observed;i nstead ent-kaurene diterpenoid (+ +)-12-hydroxy-1a,6a-diacetoxy-ent-kaura-9 (11), 16-dien-15-one (4)w as obtained as the sole product even in the presence of O 2 and photosensitizer ( Table 1, entries 1-3). [6,15] Surprisingly, when (À)-2 was exposed to UV light (365 nm), (+ +)-1 was not observed;i nstead ent-kaurene diterpenoid (+ +)-12-hydroxy-1a,6a-diacetoxy-ent-kaura-9 (11), 16-dien-15-one (4)w as obtained as the sole product even in the presence of O 2 and photosensitizer ( Table 1, entries 1-3).…”

Section: Angewandte Chemiementioning

confidence: 57%

Enantioselective Total Synthesis of (+)‐Jungermatrobrunin A

Kadonaga

Hong

et al. 2019

Angew Chem Int Ed

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Ac oncise and enantioselective total synthesis of (+ +)-jungermatrobrunin A( 1), whichf eatures au nique bicyclo[3.2.1]octene ring skeleton with an unprecedented peroxideb ridge,w as accomplished in 13 steps by making use of al ate-stage visible-light-mediated Schenck ene reaction of (À)-1a,6a-diacetoxyjungermannenone C( 2). Along the way, aU V-light-induced bicyclo[3.2.1]octene ring rearrangement afforded (+ +)-12-hydroxy-1a,6a-diacetoxy-ent-kaura-9(11),16dien-15-one (4). These divergent photo-induced skeletal rearrangements support apossible biogenetic relationship between (+ +)-1,(À)-2,and (+ +)-4.

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Section: Angewandte Chemiementioning

confidence: 57%

Enantioselective Total Synthesis of (+)‐Jungermatrobrunin A

Kadonaga

Hong

et al. 2019

Angew Chem Int Ed

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“…Vlad and co‐workers developed regio and stereoselective syntheses of (+)‐6‐ketoeuryfuran ( 71 ), (+)‐6‐ketowinterin ( 72 ), and (‐)‐7‐ketoeuryfuran ( 80 ) from easily available diterpenoids (+)‐larixyl acetate ( 66 ) and (‐)‐sclareol ( 73 ) in 2013 [36] . The main constituent of the oleoresin of Larix decidua is (+)‐larixyl acetate ( 66 ) [37,38] and (‐)‐sclareol ( 73 ) was available from the flower of Salvia sclarea [39] .…”

Section: Semisynthesis At Room Temperature and Pharmacological Aspectsmentioning

confidence: 99%

“…6‐Ketoeuryfuran ( 71 ) was also synthesized in 72 % overall yield from the same starting compound 6α‐acetoxydiene ( 67 ) via a different route including three steps out of four occurred at room temperature. They were also able to synthesize relatively stable drimanic anhydride 6‐ketowinterin ( 72 ) from 6‐ketoeuryfuran ( 71 ) over two steps successfully [36] (Scheme 12).…”

Section: Semisynthesis At Room Temperature and Pharmacological Aspectsmentioning

confidence: 99%

Diterpenoids: Natural Distribution, Semisynthesis at Room Temperature and Pharmacological Aspects‐A Decade Update

Majhi¹

2020

ChemistrySelect

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Diterpenoids are a wide and structurally diverse class of natural products and secondary metabolites obtained from four isoprene units joined in a head‐tail fashion. It has been extensively investigated that a semisynthesis is an essential tool for enhancing the biological activity of starting natural products. Different diterpenoids have been employed as starting materials for the synthesis of bioactive semisynthetic derivatives at room temperature in this review. Energy plays a profound role in chemical transformations. However, according to the sixth principle of green chemistry, the most successful route to save energy is to develop strategies/protocols that are able enough to perform the reactions at ambient temperature. This review is aimed to offer an overview of natural distributions of diterpenoids, design, and semisynthesis of diterpenoids at room temperature, and highlights biological activities of semisynthetic derivatives for the first time from 2010–2019.

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“…Having efficiently synthesized (À)-2,w et urned to investigate the photo-induced singlet oxygen Schenck ene reaction to construct the peroxide bridge of (+ +)-1. [6,15] Surprisingly, when (À)-2 was exposed to UV light (365 nm), (+ +)-1 was not observed;i nstead ent-kaurene diterpenoid (+ +)-12-hydroxy-1a,6a-diacetoxy-ent-kaura-9 (11), 16-dien-15-one (4)w as obtained as the sole product even in the presence of O 2 and photosensitizer (Table 1, entries 1-3). However,u pon UV irradiation of (À)-2 at 365 nm in MeOH, (+ +)-4 was isolated in 14 %yield along with 81 %recovered (À)-2 (Table 1, entry 4).…”

Section: Angewandte Chemiementioning

confidence: 99%