Diastereoselective addition of monoorganocuprates to a chiral fumarate: reaction development and synthesis of (−)-dihydroprotolichesterinic acid

Hethcox, J. Caleb; Shanahan, Charles S.; Martin, Stephen F.

doi:10.1016/j.tet.2015.05.023

Cited by 7 publications

(2 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This trans -stereochemistry of 10 was confirmed observing a large J coupling (16.9 Hz) for the E-alkene hydrogens. Alternatively, when anhydrous lithium chloride was used instead of DMAP, we obtained maleate product 11a ( J = 13.5 Hz) in moderate yield . Precursor 11b (R = m -F) was also synthesized from m -fluoro-benzaldehyde using the same approach.…”

Section: Resultsmentioning

confidence: 99%

“…Alternatively, when anhydrous lithium chloride was used instead of DMAP, we obtained maleate product 11a (J = 13.5 Hz) in moderate yield. 15 Precursor 11b (R = m-F) was also synthesized from m-fluoro-benzaldehyde using the same approach. To render the dienophile more electrophilic, we hypothesized that replacing maleate hydrogens with bromine may enhance dienophile reactivity with the tethered styryl diene.…”

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Intramolecular Heteroatom and Styryl Diels–Alder Reactions, Asymmetric Cycloadditions of Chiral 3-Phenylallyl Maleic Esters

Mpaata,

Miller,

Bonsrah

et al. 2024

J. Org. Chem.

View full text Add to dashboard Cite

Polycyclic aryl naphthalene and tetralin dihydro arylnaphthalene lactone lignans possess anticancer and antibiotic activity. Related furo [3,4-c]pyranones, typified by the sequester-terpenoid isobolivianine, show similar antiproliferative bioactivity. Efficient syntheses of compounds featuring these polycyclic cores have proven challenging due to low yields and poor stereoselectivity. We report the synthesis of chiral cinnamyl but-2-enanoates and 3,3-diphenylallyl-but-2-enoates 1 as new Diels− Alder substrates. These compounds undergo [4 + 2]-cycloadditions to give furo[3,4-c]pyranones 2 in good yield (70%) and diastereoselectivity (7:1), together with naphthyl 3 and dihydronaphthyl tetralins 4 as minor products. Molecular structures and stereochemistries of the major products were verified using X-ray diffraction. Density functional theory calculations revealed that the cycloaddition process involves a bispericyclic/ambimodal process where there is a single transition state that leads to both intramolecular styryl Diels−Alder (ISDA) 3, 4 and intramolecular hetero Diels−Alder (IHDA) cycloadducts 2. With the elevated temperature conditions after cycloaddition, the resulting ISDA cycloadduct either undergoes [3,3]-sigmatropic rearrangement to the more stable major IHDA product or aromatization leading to the phenyltetralin.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Intramolecular Heteroatom and Styryl Diels–Alder Reactions, Asymmetric Cycloadditions of Chiral 3-Phenylallyl Maleic Esters

Mpaata,

Miller,

Bonsrah

et al. 2024

J. Org. Chem.

View full text Add to dashboard Cite

show abstract

Evolution of Strategies in Paraconic Acids Synthesis

2020

View full text Add to dashboard Cite

Various syntheses of different paraconic acids over the last seventeen years have been abstracted here. Paraconic acids have either a methylene or methyl group at the 4-position of the γ-butyrolactone with a common C-3 carboxylic acid group and a long alkyl chain. Several possibilities of relative configurations give rise to distinct set of paraconic acids, which are also categorized in this review. Various strategies based on chiral catalytic methods, chiral pool, chiral auxiliary, resolution and other methods were engaged in the synthesis of different paraconic acids. A few members are yet to be synthesized and this compilation might entice future synthetic attempts on them.

show abstract

ChemInform Abstract: Diastereoselective Addition of Monoorganocuprates to a Chiral Fumarate: Reaction Development and Synthesis of (‐)‐Dihydroprotolichesterinic Acid.

2015

View full text Add to dashboard Cite

Diastereoselective Addition of Monoorganocuprates to a Chiral Fumarate: Reaction Development and Synthesis of (-)-Dihydroprotolichesterinic Acid. -Recently reported diastereoselective conjugate addition of monoorganocuprates to chiral -alkoxycrotonates and fumarates is applied to the shortest total synthesis of (-)-dihydroprotolichesterinic acid (VI) to date. Attempts to prepare pilocarpine from chiral succinate (IIIb) result in the formation of (IX) instead. Under similar conditions, reaction of (I) with aryl bromide (X) gives aryl succinate (XI) instead of expected antrodin E. -(HETHCOX, J. C.; SHANAHAN, C. S.; MARTIN*, S. F.; Tetrahedron 71 (2015) 37, 6361-6368, http://dx.

show abstract

Diastereoselective addition of monoorganocuprates to a chiral fumarate: reaction development and synthesis of (−)-dihydroprotolichesterinic acid

Cited by 7 publications

References 58 publications

Intramolecular Heteroatom and Styryl Diels–Alder Reactions, Asymmetric Cycloadditions of Chiral 3-Phenylallyl Maleic Esters

Intramolecular Heteroatom and Styryl Diels–Alder Reactions, Asymmetric Cycloadditions of Chiral 3-Phenylallyl Maleic Esters

Evolution of Strategies in Paraconic Acids Synthesis

ChemInform Abstract: Diastereoselective Addition of Monoorganocuprates to a Chiral Fumarate: Reaction Development and Synthesis of (‐)‐Dihydroprotolichesterinic Acid.

Contact Info

Product

Resources

About