Synthesis of 4-ylidenebutenolides from 2-trimethylsiloxyfuran

Asaoka, Morio; Yanagida, Noboru; Ishibashi, Keiji; Takei, Hisashi

doi:10.1016/s0040-4039(01)82929-4

Cited by 60 publications

(22 citation statements)

References 7 publications

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“…60 This strategy was not without risks given the potential functional group incompatibility issues since the expected low reactivity of ketone substrates in a Mukaiyama aldol reaction would necessitate the use of strong Lewis or Brönsted acids. Furthermore, the stereochemical outcome of the reaction was unclear.…”

Section: Resultsmentioning

confidence: 99%

Total Synthesis of the Spirocyclic Imine Marine Toxin (−)-Gymnodimine and an Unnatural C4-Epimer

Kong¹,

Moussa²,

Lee³

et al. 2011

J. Am. Chem. Soc.

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The first total synthesis of the marine toxin (−)-gymnodimine (1) has been accomplished in a convergent manner. A highly diastereo- and enantioselective exo-Diels–Alder reaction catalyzed by a bis-oxazoline Cu(II) catalyst enabled rapid assembly of the spirocyclic core of gymnodimine. The preparation of the tetrahydrofuran fragment utilized a chiral auxiliary based anti-aldol reaction. Two major fragments, spirolactam 56 and tetrahydrofuran 55, were then coupled through an efficient Nozaki–Hiyama–Kishi reaction. An unconventional, ambient temperature t-BuLi-initiated intramolecular Barbier reaction of alkyl iodide 64 was employed to form the macrocycle. A late stage vinylogous Mukaiyama aldol addition of a silyloxyfuran to a complex cyclohexanone 83 appended the butenolide and a few additional steps provided (−)-gymnodimine (1). A diastereomer of the natural product was also synthesized, C4-epi-gymnodimine (90), derived from the vinylogous Mukaiyama aldol addition.

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Section: Resultsmentioning

confidence: 99%

Total Synthesis of the Spirocyclic Imine Marine Toxin (−)-Gymnodimine and an Unnatural C4-Epimer

Kong¹,

Moussa²,

Lee³

et al. 2011

J. Am. Chem. Soc.

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“…11 ) Various alkylidene-2(5H)furanones were synthesized through a method developed by Asaoka and Takei. 12 ) 3-Methyl-and 4-methyl-5-methylene-2(5H)furanones were prepared by a modified method of Young et al 13 )…”

Section: And Discussionmentioning

confidence: 99%

“…A nonconjugated 4,5-dihydro-5-methylene-2-(3H)furanone (12) was inactive for both assays. As shown in Fig.…”

Section: =0=0 -Voa~ysoh2mentioning

confidence: 98%

Structure-Activity Relationship and Design of an Antimutagen against the UV-Induced Mutation ofEscherichia coli

Kakinuma

Koike

Ishibashi

et al. 1986

Agricultural and Biological Chemistry

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“…Clearly, this widely studied approach for aldehydes has not led to similar levels of success when employed with ketones. Apparently, low reactivity and low selectivity is the origin of this disparity [133,148,149]. A study by Romo showed that high diastereoselectivities could be obtained with ketones when choosing 3-methyl-2-(tert-butyldimethylsilyloxy) furan; however, high quantities of Lewis acids (0.4-3.0 equiv.)…”

Section: Bismuth-catalyzed Mukaiyama Aldol Reaction Of Silyloxyfuransmentioning

confidence: 99%

Bismuth-Catalyzed Addition of Silyl Nucleophiles to Carbonyl Compounds and Imines

Ollevier

2011

Bismuth-Mediated Organic Reactions

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Bismuth triflate was found to be an efficient catalyst both in the Mannich-type reaction of silyl enolates and in the Sakurai reaction of allyltrimethylsilane with N-alkoxycarbonylamino sulfones. The reactions proceeded smoothly with a low catalyst loading of Bi(OTf)(3)·4H(2)O (0.5-5.0 mol%) to afford the corresponding protected β-amino carbonyl compounds and homoallylic amines in very good yields (up to 96%). The latter compounds could also be obtained via a bismuth-mediated three-component reaction. We have also developed an efficient vinylogous Mukaiyama aldol reaction of 2-(trimethylsilyloxy)furan with various aromatic aldehydes mediated by bismuth triflate in a low catalyst loading (1 mol%). The reaction proceeds rapidly and affords the corresponding 5-[hydroxy(aryl)methyl]furan-2(5H)-ones in high yields with good to very good diastereoselectivities (diastereoisomeric ratios>98:2). Such selectivities, although previously reported with other Lewis acids, could be achieved with a much lower catalyst loading. 5-[Hydroxy(alkyl)methyl]furan-2(5H)-ones derived from ketones could also be obtained with good diastereoselectivities. The vinylogous Mukaiyama aldol reaction has also been extended to 2,2-dimethyl-6-methylene-4-(trimethyl-silyloxy)-1,3-diox-4-ene using 1 mol% of Bi(OTf)(3)·4H(2)O.

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Synthesis of 4-ylidenebutenolides from 2-trimethylsiloxyfuran

Cited by 60 publications

References 7 publications

Total Synthesis of the Spirocyclic Imine Marine Toxin (−)-Gymnodimine and an Unnatural C4-Epimer

Total Synthesis of the Spirocyclic Imine Marine Toxin (−)-Gymnodimine and an Unnatural C4-Epimer

Structure-Activity Relationship and Design of an Antimutagen against the UV-Induced Mutation ofEscherichia coli

Bismuth-Catalyzed Addition of Silyl Nucleophiles to Carbonyl Compounds and Imines

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