Derivatives of 1-methoxy-3-trimethylsilyloxy-1,3-butadiene for Diels-Alder reactions

Danishefsky, Samuel J.; Yan, Changzeng; Singh, Rajendra K.; Gammill, Ronald B.; McCurry, Patrick M.; Fritsch, Nancy; Clardy, Jon

doi:10.1021/ja00517a037

Cited by 131 publications

(64 citation statements)

References 10 publications

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“…Fortunately, the MT value of the ester can be calculated validly, since only k p (partial rate constants for rearrangement) are used in the determination. The ketone group in 4-methyl-4-acetyl-2,5-cyclohexadienone undergoes only fragmentation 17 . The carboxylic acid group undergoes easy fragmentation.…”

Section: Resultsmentioning

confidence: 99%

Fragmentation vs rearrangement of the amide and thioester groups in 4,4-disubstituted cyclohexadienones

Marx¹,

Merken²

2004

Arkivoc

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Migration of electron-withdrawing substituents in carbocations normally occurs in preference to other common substituents that are normally very good migrating groups, if the electronwithdrawing group contains a π bond. This study represents the first investigation of the amide (diethylamido) and thioester (thiocarbethoxy) substituents in the dienone-phenol rearrangement reaction. In aqueous acid, the dienones 6b and 6c were found to fragment instead of to undergo rearrangement. A mechanistic rationalization is given.

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Section: Resultsmentioning

confidence: 99%

Fragmentation vs rearrangement of the amide and thioester groups in 4,4-disubstituted cyclohexadienones

Marx¹,

Merken²

2004

Arkivoc

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“…1-Methoxy-2-methyl-3-trimethylsilyloxy-1,3-butadiene 14 (3), which has been previously used in the asymmetric aza-Diels-Alder reaction, 15 has not been extensively investigated in the hetero-Diels-Alder reaction of aldehydes. To investigate the influence of the diene, 3 was reacted with p-nitrobenzaldehyde in the presence of dirhodium(II) carboxamidate catalysts (Table 3).…”

Section: Figure 2 Mukaiyama Aldol Adductmentioning

confidence: 99%

Influence of the Diene in the Hetero-Diels-Alder Reaction Catalyzed by Dirhodium(II) Carboxamidates

Valenzuela¹,

Doyle²,

Hedberg³

et al. 2004

Synlett

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“…Herein, we report that high regioselectivities could be achieved with this class of substrates, resulting in efficient formation of β-alkoxyenone products, which are synthetically versatile and can serve as precursor to the Danishefsky’s diene [10] and its congeners, [11] functionalized tetrahydropyrans, [12] and enynones. [13]…”

Section: Introductionmentioning

confidence: 99%

Gold-catalyzed oxidation of propargylic ethers with internal C–C triple bonds: Impressive regioselectivity enabled by inductive effect

D'Souza

Nelson

et al. 2014

Journal of Organometallic Chemistry

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Inductive perturbations of C-C triple bonds are shown to dictate the regiochemistry of gold-catalyzed oxidation of internal C-C triple bonds in the cases of propargylic ethers, resulting in highly regioselective formation of β-alkoxy-α,β-unsaturated ketones (up to >50/1 selectivity) via α-oxo gold carbene intermediates. Ethers derived from primary propargylic alcohols can be reliably transformed in good yields, and various functional groups are tolerated. With substrates derived from secondary propargylic alcohols, the development of a new P,N-bidentate ligand enables the minimization of competing alkyl group migration to the gold carbene center over the desired hydride migration; the preferred migration of a phenyl group, however, results in efficient formation of a α-phenyl-β-alkoxy-α,β-unsaturated ketone. These results further advance the surrogacy of a propargyl moiety to synthetically versatile enone function with reliable and readily predictable regioselectivity.

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Derivatives of 1-methoxy-3-trimethylsilyloxy-1,3-butadiene for Diels-Alder reactions

Cited by 131 publications

References 10 publications

Fragmentation vs rearrangement of the amide and thioester groups in 4,4-disubstituted cyclohexadienones

Fragmentation vs rearrangement of the amide and thioester groups in 4,4-disubstituted cyclohexadienones

Influence of the Diene in the Hetero-Diels-Alder Reaction Catalyzed by Dirhodium(II) Carboxamidates

Gold-catalyzed oxidation of propargylic ethers with internal C–C triple bonds: Impressive regioselectivity enabled by inductive effect

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