One-pot conversion of olefins to carbonyl compounds by hydroboration / NMO-TPAP oxidation

Yates, Matthew H.

doi:10.1016/s0040-4039(97)00476-0

Cited by 30 publications

(15 citation statements)

References 5 publications

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“…Tetrahydrofuran synthesis from geraniol acetate proceeded with higher yields with 16 and 19 than that reported with TPAP . In addition, the tandem hydroboration‐oxidation reaction proceeded in good yield and consistent with the use of TPAP in our hands, but lower than that previously reported …”

Section: Methodssupporting

confidence: 90%

“…[2a] For example, diol cleavage to give dialdehydes [16] or dicarboxylic acids, [17] oxidation of secondary amines to imines, [18] sulfidest os ulfones, [19] and hydroxyamines to nitrones. [20] Additional examples include onepot hydroboration-oxidationo fa lkenes, [21] conversion of etherst oe sters, [8] double bond isomerization, [22] and the formationo fh eterocyclic ring systems, such as tetrahydrofurans, [23] pyridines, [24] triazoles, [25] lactams [26] and lactones. [27] AlthoughT PAP(4)i sd escribed as air-stable, and that it can be stored indefinitely in the cold (i.e.…”

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confidence: 99%

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ATP3 and MTP3: Easily Prepared Stable Perruthenate Salts for Oxidation Applications in Synthesis

Moore

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Bernhardt

et al. 2018

Chemistry A European J

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The Ley-Griffith tetra-n-propylammonium perruthenate (TPAP) catalyst has been widely deployed by the synthesis community, mainly for the oxidation of alcohols to aldehydes and ketones, but also for a variety of other synthetic transformations (e.g. diol cleavage, isomerizations, imine formation and heterocyclic synthesis). Such popularity has been forged on broad reaction scope, functional group tolerance, mild conditions, and commercial catalyst supply. However, the mild instability of TPAP creates preparation, storage, and reaction reproducibility issues, due to unpreventable slow decomposition. In search of attributes conducive to catalyst longevity an extensive range of novel perruthenate salts were prepared. Subsequent evaluation unearthed a set of readily synthesized, bench stable, phosphonium perruthenates (ATP3 and MTP3) that mirror the reactivity of TPAP, but avoid storage decomposition issues.

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Section: Methodssupporting

confidence: 90%

mentioning

confidence: 99%

ATP3 and MTP3: Easily Prepared Stable Perruthenate Salts for Oxidation Applications in Synthesis

Moore

Read

Bernhardt

et al. 2018

Chemistry A European J

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“…With cyclopentene product 27 in hand, diketone 7 was obtained as a diastereoisomeric mixture through a one‐pot hydroboration/oxidation process . Hydrogenolysis of 7 with Pd(OH) 2 /C in the presence of H 2 afforded alcohol 33 in 91 % yield (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…Total synthesis of (À À)-huperzine Q (1) With cyclopentenep roduct 27 in hand, diketone 7 was obtained as ad iastereoisomeric mixture through ao ne-pot hydroboration/oxidation process. [21] Hydrogenolysis of 7 with Pd(OH) 2 /C in the presence of H 2 afforded alcohol 33 in 91 % yield (Scheme 5). Inspired by the landmark work done by the Heathcock group during their fawcettimine synthesis, [22] we envisagedt hat the aminal moiety of (À)-huperzine Q( 1)c ould be accessedf rom 33 through aC 4e pimerization/cyclization se-quence.…”

Section: Retrosynthetic Analysismentioning

confidence: 99%

Divergent Total Syntheses of (−)‐Huperzine Q, (+)‐Lycopladine B, (+)‐Lycopladine C, and (−)‐4‐epi‐Lycopladine D

Hong

et al. 2017

Chemistry An Asian Journal

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We report herein our synthetic efforts towards the divergent syntheses of (À)-huperzine Q( 1), (+ +)-lycopladine B (2), (+ +)-lycopladine C( 3), and (À)-lycopladine D( 4). The 10-step total synthesis of (À)-huperzine Q( 1)a nd the first total syntheses of (+ +)-lycopladines B( 2)a nd C( 3)w ere accomplished through as eries of cascade reactions. Our approach involved aM ichael addition/aldol/intramolecular C-alkylation sequence to forge the 6/9 spirocycle ring, and this was followed by an ethylene-accelerated carbonyl-olefin metathesis to construct the common 6/5/9 ring system.F inally,l atestage enamine bromofunctionalization enabled us to access (À)-huperzine Q( 1), (+ +)-lycopladine B( 2), and (+ +)-lycopladine C( 3), and at andem C4-epimerization/retro-Claisenc ondensation furnished (À)-4-epi-lycopladine D( 63). IntroductionThe Lycopodium alkaloids are al arge family of complex natural products.N early 300 compounds have been isolated so far. [1] Owing to their intricate polycyclic skeletons andd iverse bioactivities, the total syntheses of these alkaloids have attracted broad attention from the synthetic community in recent years. [2] Among these compounds, (À)-huperzine Q( 1), (+ +)-lycopladine B( 2), (+ +)-lycopladine C( 3), and (À)-lycopladine D( 4) are four structurally relatedf awcettimine-type alkaloids (Figure 1). HuperzineQ (1)w as isolatedf rom Huperzia serrata by Zhu and co-workersi n2 002, and it possessesa nu nprecedented pentacyclic ring system and an aminal moiety. [3] The Takayama group [4] and the Zhao group [5] reported the total syntheseso f1 in 2011a nd 2015, respectively.( + +)-Lycopladine B (2), (+ +)-lycopladine C( 3), and (À)-lycopladine D( 4)w ere isolated from Lycopodium complanatum by Kobayashi and co-workers in 2006. [6] Whereasb oth (+ +)-lycopladines B( 2)a nd C( 3) contain au nique tetracyclic skeleton with ad ienamine moiety, (À)-lycopladine D( 4)c onsists of ap entacyclic core structure with ac arbinolamine lactone core. In 2013, Zhao and co-workers achievedt he first total synthesis of (À)-lycopladine D( 4). [7] Herein, we describe af ull account of our divergents yntheses of (À)-huperzine Q( 1), (+ +)-lycopladine B( 2), and (+ +)-lycopladine C( 3) [8] as wella so ur synthetic efforts towards (À)-lycopladine D( 4). Retrosynthetic analysisOur retrosynthetic analysisf or (À)-huperzine Q( 1), (+ +)-lycopladine B( 2), (+ +)-lycopladine C( 3), and (À)-lycopladine D( 4)i s outlined in Scheme 1. We envisioned that the aminal moietyi n 1 and the dienamine moieties in 2 and 3 could be derived from enamine intermediates 5 and 6,r espectively.W hereas both 5 and 6 could arise from 7 by aC 4-epimerization/cyclization sequence, diketone 7 could also potentially serve as ac ommon synthetic intermediate for the synthesis of (À)-lycopladine D( 4)t hrough aldehyde 10.T he cyclopentanone ring in 7 could be constructedf rom spirocyclic diketone 8,w hich could be readily accessed from enone 9 through our previously developed Michael addition/aldol/C-alkylation method.Initial synthe...

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“…Enantioselective reduction of ketones by BMS catalyzed by oxazaphospholidine oxides(16), instead of the more conventional oxazaborolidines, has been reported by Buono and co-workers (ee = 25-94%) 98. One-pot conversion of olefins to carbonyl compounds by hydroboration/oxidation has been reported by Yates, in yields of 50-98% (eq 27) 99. …”

mentioning

confidence: 96%

Borane Dimethyl Sulfide

Zaidlewicz

Baum

Srebnik

2006

Encyclopedia of Reagents for Organic Synthesis

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One-pot conversion of olefins to carbonyl compounds by hydroboration / NMO-TPAP oxidation

Cited by 30 publications

References 5 publications

ATP3 and MTP3: Easily Prepared Stable Perruthenate Salts for Oxidation Applications in Synthesis

ATP3 and MTP3: Easily Prepared Stable Perruthenate Salts for Oxidation Applications in Synthesis

Divergent Total Syntheses of (−)‐Huperzine Q, (+)‐Lycopladine B, (+)‐Lycopladine C, and (−)‐4‐epi‐Lycopladine D

Borane Dimethyl Sulfide

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