Ligand-assisted nucleophilic additions. Control of site and face attack of nucleophiles on 4-oxido enones

Solomon, M.; Jamison, W.C.L.; McCormick, Michael S.; Liotta, Dennis; Cherry, David; Mills, John; Shah, Rekha D.; Rodgers, James D.; Maryanoff, Cynthia A.

doi:10.1021/ja00219a079

Cited by 67 publications

(25 citation statements)

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“…Selective epoxidation followed by reductive epoxide opening furnished the desired alcohol 73 [ 72 ]. Alcohol-directed 1,4-reduction using LiAlH 4 [ 73 ] followed by ether formation gave methyl ether 74 . Reduction of the remaining ketone moiety gave the equatorial alcohol exclusively.…”

Section: Reviewmentioning

confidence: 99%

Recent applications of the divinylcyclopropane–cycloheptadiene rearrangement in organic synthesis

Krüger¹,

Gaich²

2014

Beilstein J. Org. Chem.

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Section: Reviewmentioning

confidence: 99%

Recent applications of the divinylcyclopropane–cycloheptadiene rearrangement in organic synthesis

Krüger¹,

Gaich²

2014

Beilstein J. Org. Chem.

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“…5 % of the applied phenyl lithium); 2-4 (petroleum ether:benzene = 10:1. (2) 1757 (3) 44(1) C (6) 6638 (3) 4448 (2) 1859 (3) 46(1) C (7) 3804 (4) 2996 (2) 546(4) 62(1) C (8) 3213 (4) 3282 (3) 1408 (4) 92(2) C (9) 2832 (4) 3131 (2) -819(4) 88(2) C (10) 4006 (5) 2174 (2) 733 (6) 127(2) C (ll) 8123 (3) 2933 (2) 532 (3) 43(1) C ( 12) 8482 (4) 2352 (2) 1376 (3) 52(1) C (13) 9433 (4) 1869 (2) 1434 (4) 62(1) C ( 14) 10047 (4) 1964 (2) 664 (4) 64(1) C (15) 9683 (4) 2528 (2) -183(4) 61(1) C ( 16) 8734 (4) 3005 (2) -232 (3) 49(1) C ( 17) 8898 (4) 4334 (2) 1868 (3) 47(1) C (18) 10097 (4) 4044 (2) 2608(4) 59(1) C ( 19) 11219 …”

Section: 6-di-tert-butyl-4-hydroxy-4-methyl-3-( 4-tolyl )-unclassified

“…tolyl)-4-exomethylene-cyclohexa-2,5-diene(8) 2.0 g (8 mmol) of para-quinol la (R = Me), treated with 2.5 equivalents of 4-tolyllithium as described above. mother liquor, a second fraction was ob tained: 0.2 g (8%)8, m. p. 148-149 °C (from petroleum ether).…”

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confidence: 99%

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1,4-Addition of Lithium Organyls to para-Quinols / Structure Determination of 2,6-Di-tert-butyl-4-hydroxy-4,5-diphenylcyclohex-2-en-1-one

Henes

Rieker

Neumayer

et al. 1996

Zeitschrift Für Naturforschung B

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Addition of lithium organyls to sterically hindered para-quinols leads to 1,2-or 1,4-adducts. The 1,4-addition prevails, if the 4-substituents in the quinol and the organic group in the lithium organyl are large. Four 1,4-addition products (2-cyclohex-2-en-l-ones) are synthesized and their structures investigated by NMR spectroscopy. The aryl groups at C-4 and C-5 acquire equatorial positions, the alkyl group at C-6 is bisectional. These results are confirmed by Xray analysis of 2,6-di-terr-butyl-4-hydroxy-4,5-diphenylcyclohex-2-en-1 -one, revealing a twist boat conformation of the cyclohexene ring.

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“… 10 Attempted allylic alcohol isomerization 11 by utilizing 1,4-diol 8 was not possible due to the inherent instability of such systems (spontaneous aromatization). Finally, efforts centering on a tandem 1,2-/1,4-addition 12 to silyl-dienone 9 ( 13 ) failed due to the tendency of silyl lithium reagents to reduce quinones rather than add to them. Collectively, these failures led us to the simplest possible approach: a conjugate addition to a substituted quinone.…”

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Antroquinonol A: Scalable Synthesis and Preclinical Biology of a Phase 2 Drug Candidate

et al. 2015

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The fungal-derived Taiwanese natural product antroquinonol A has attracted both academic and commercial interest due to its reported exciting biological properties. This reduced quinone is currently in phase II trials (USA and Taiwan) for the treatment of non-small-cell lung carcinoma (NSCLC) and was recently granted orphan drug status by the FDA for the treatment of pancreatic cancer and acute myeloid leukemia. Pending successful completion of human clinical trials, antroquinonol is expected to be commercialized under the trade name Hocena. A synthesis-enabled biological re-examination of this promising natural product, however, reveals minimal in vitro and in vivo antitumor activity in preclinical models.

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Ligand-assisted nucleophilic additions. Control of site and face attack of nucleophiles on 4-oxido enones

Cited by 67 publications

References 0 publications

Recent applications of the divinylcyclopropane–cycloheptadiene rearrangement in organic synthesis

Recent applications of the divinylcyclopropane–cycloheptadiene rearrangement in organic synthesis

1,4-Addition of Lithium Organyls to para-Quinols / Structure Determination of 2,6-Di-tert-butyl-4-hydroxy-4,5-diphenylcyclohex-2-en-1-one

Antroquinonol A: Scalable Synthesis and Preclinical Biology of a Phase 2 Drug Candidate

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