Efficient total synthesis of (+)-exo-, (−)-endo-brevicomin and their derivatives via asymmetric organocatalysis and olefin cross-metathesis

Kim, Sung‐Gon; Park, Tae-Ho; Kim, Bong Jin

doi:10.1016/j.tetlet.2006.06.170

Cited by 34 publications

(11 citation statements)

References 44 publications

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“…An interesting one-pot method for the synthesis of the precursor of Brevicomin by coupling l -proline-catalyzed α-aminoxylation of aldehyde with indium-mediated allylation was reported by Kim and co-workers (Scheme ) . However, the allylation step proceeded with poor diastereoselectivity (3:2 syn/anti), although the first aminoxylation step is highly enantioselective (∼98% ee).…”

Section: Allylindium Reagentsmentioning

confidence: 99%

Organoindium Reagents: The Preparation and Application in Organic Synthesis

et al. 2012

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allylation performed in aqueous media, an efficient synthesis of highly functionalized lactones was realized in good yields (64− 77%, Scheme 29). 238 However, the chirality installed during the first step almost had no influence on the second step, thus resulting in poor diastereoselectivity in the subsequent allylation reaction (1:1−2:1 dr).In situ formation of aldehyde from the oxidation of alcohol followed by one-pot indium-mediated allylation also provides an alternative method for the synthesis of homoallylic alcohol. Recently, Yadav and co-workers developed such a one-pot sequence by using chloramines-T (sodium salt of Nchlorotosylamide) as oxidant in the presence of a catalytic amount of FeCl 3 in CH 2 Cl 2 , giving rise to homoallylic alcohols in good to excellent yields (Scheme 30). 239 It is noteworthy that the generated byproduct of TsNH 2 (from the reduction of chloramines-T) may react with the in situ-formed aldehydes to give intermediates of N-tosylimines in the presence of 4 Å molecular sieve under refluxing; the thus-formed N-tosylimines subsequently underwent one-pot indium-mediated allylation to produce homoallylic amines in 60−80% yields. Later, a similar one-pot, two-step sequence for the synthesis of homoallylic alcohols via a galactose oxidase-mediated chemo-enzymatic oxidation of benzyl and cinnamyl alcohols to the corresponding Scheme 23 Scheme 24 Scheme 25 Scheme 26 Scheme 27 Scheme 28 Scheme 29 Scheme 30 Chemical Reviews Review dx.

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Section: Allylindium Reagentsmentioning

confidence: 99%

Organoindium Reagents: The Preparation and Application in Organic Synthesis

et al. 2012

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“…Other target molecules which had been successfully synthesized using proline catalyzed α-aminoxylation as one of the key steps include halipeptin A [ 104 ], (+)- exo - and (–)- endo -brevicomins [ 105 ], linezolid and eperezolid [ 106 ], levetiracetam [ 107 ], ( S , S )-ethambutol [ 108 ], (+)-harzialactone A and ( R )-(+)-4-hexanolide [ 109 ], ( R )-seleginine [ 110 ], ( S )-propanolol and ( S )-naftopidil [ 111 ], (+)-disparlure and its trans -isomer [ 112 ], (-)-anisomycin [ 59 ] and (1 R ,3 S )-thysanone, a HRV 3C-protease inhibitor [ 113 ].…”

Section: α-Aminoxylation Reactionsmentioning

confidence: 99%

Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds

2010

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Organocatalytic asymmetric α-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects and synthetic applications of α-oxidation, hydroxylation, aminoxylation, amination, hydrazination, hydroxyamination and related α-heteroatom functionalization of aldehydes, ketones and related active methylene compounds published during 2005–2009.

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“…For instance, (S,S)-ethambutol (23) [26], (R)-selegiline (24) [27] and (-)-anisomycin (27) [30], which could be alternatively synthesized by means of an organocatalyzed α-amination reaction (see section 2.2, Figure 2), could be prepared with similar results by using this transformation. In a similar way, the antiinflammatory halipeptin A (111) [94], the antitumor agents tarchonanthuslactone (112) [95], (+)-cytotrienin A [96] and (+)-harzialactone A and (R)-(+)-4-hexanolide [97], the antibacterials linezolid (113) and eperezolid [98], the antiepileptic drugs levetiracetam (114) [99], the pheromones (-)-endo-brevicomin (115) [100], (+)-disparlure [101] and (2S,3S)-2-hydrohyhexylcyclopentanone [102], and the enzyme inhibitors (+)-panephenanthrin (116) [103], and the β-adrenergic blockers (S)-propranolol (117) and (S)-naftopidil [104] have been synthesized using in all cases the α-aminoxylation of aldehydes as a key step (Figure 12). …”

Section: Scheme 24mentioning

confidence: 95%

Recent Advances on the Organocatalyzed Enantioselective α-heterofunctionalization of Carbonyl Compounds

Guillena¹,

Ramón

2011

COC

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Abstract:This review covers literature on organocatalyzed enantioselective α-heterofunctionalization of carbonyl compounds from 2006 to 2009. In this review, we will consider those reactions in which a new carbon-heteroatom bond is formed using a chiral organic molecule as catalyst, excluding those processes, which involve the modification on the hybridization of a previously functionalized carbonyl compound. Using this straightforward synthetic strategy, a wide range of valuable chiral building blocks such as α-amino acids, α-amino alcohols, epoxides, 1,2-diols, α-sulfenylated, α-selenenylated and α-halogenated carbonyl derivatives can be obtained by this simple and advantageous methodology.

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Efficient total synthesis of (+)-exo-, (−)-endo-brevicomin and their derivatives via asymmetric organocatalysis and olefin cross-metathesis

Cited by 34 publications

References 44 publications

Organoindium Reagents: The Preparation and Application in Organic Synthesis

Organoindium Reagents: The Preparation and Application in Organic Synthesis

Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds

Recent Advances on the Organocatalyzed Enantioselective α-heterofunctionalization of Carbonyl Compounds

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Efficient total synthesis of (+)-exo-, (−)-endo-brevicomin and their derivatives via asymmetric organocatalysis and olefin cross-metathesis

Cited by 34 publications

References 44 publications

Organoindium Reagents: The Preparation and Application in Organic Synthesis

Organoindium Reagents: The Preparation and Application in Organic Synthesis

Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds

Recent Advances on the Organocatalyzed Enantioselective &#945;-heterofunctionalization of Carbonyl Compounds

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Recent Advances on the Organocatalyzed Enantioselective α-heterofunctionalization of Carbonyl Compounds