New Chiral Pool Approach to Anthracyclinones. The Stereoselective Synthesis of Idarubicinone

Achmatowicz, O.; Szechner, Barbara

doi:10.1021/jo026354l

Cited by 21 publications

(9 citation statements)

References 23 publications

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“…The title compound, (I), is an intermediate in the enantioselective synthesis of an anthracycline-like product. Compound (I) possesses obvious similarities to both idarubicin (II) and daunorubicin (III), and the stereochemistry of the stereogenic centers at C3 and C1 are exactly identical to that of the anthracycline antibiotics (Chen & Liu, 1994;Champoux, 2001;Achmatowicz & Szechner, 2002). The product was obtained in reasonable yield and diastereoselectivity (80% yield, 74% d.e.)…”

Section: Commentmentioning

confidence: 93%

(1S,3S)-1-tert-Butyldiphenylsiloxy-3-hydroxy-3-isopropenyl-1,2,3,4-tetrahydronaphthalene

2005

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In the title compound, C29H34O2Si, the isopropenyl group is oriented trans and the OH group is cis to the tert‐butyldiphenylsiloxy (OTBDPS) group. The cyclohexane ring of the tetrahydronaphthalene system adopts a half‐chair conformation in which the stereogenic centre at the ring C3 atom is projected above the plane of the ring (3H2), minimizing steric congestion between the substituents on the ring C3 atom and the bulky OTBDPS group.

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Section: Commentmentioning

confidence: 93%

(1S,3S)-1-tert-Butyldiphenylsiloxy-3-hydroxy-3-isopropenyl-1,2,3,4-tetrahydronaphthalene

2005

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“…53 Hydroxyphthalides are intermediates for assembly of anthracyclinone-type antibiotics. 54 Of special interest is the ability of the carboxylate to introduce an allyl substituent. Reaction of N,N-diisopropylbenzamide or 2-methoxy-N,N-diethylbenzamide with allyl bromide under standard conditions (s-BuLi-TMEDA complex, -78 °C, THF) provided the bromides instead of the allylated derivatives.…”

Section: Resultsmentioning

confidence: 99%

“…In cases where DoM occurs at the position adjacent to the carboxylate group (routes A, C, and F), the primary products obtained with DMF ( 4 , 6 , 9 g ) and benzaldehyde ( 4 , 6 , 9h ) after acidic hydrolysis were directly transformed into hydroxyphthalides and lactones 11 − 16 (Figure ) . Hydroxyphthalides are intermediates for assembly of anthracyclinone-type antibiotics 4 Hydroxyphthalides and lactones 11 − 16 .…”

Section: Resultsmentioning

confidence: 99%

First General, Direct, and Regioselective Synthesis of Substituted Methoxybenzoic Acids by Ortho Metalation

et al. 2007

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New general methodology of value in aromatic chemistry based on ortho-metalation sites in o-, m-, and p-anisic acids (1-3) (Scheme 1) is described. The metalation can be selectively directed to either of the ortho positions by varying the base, metalation temperature, and exposure times. Metalation of o-anisic acid (1) with s-BuLi/TMEDA in THF at -78 degrees C occurs exclusively in the position adjacente to the carboxylate. On the other hand, a reversal of regioselectivity is observed with n-BuLi/t-BuOK. With LTMP at 0 degrees C, the two directors of m-anisic acid (2) function in concert to direct introduction of the metal between them while n-BuLi/t-BuOK removes preferentially the proton located ortho to the methoxy and para to the carboxylate (H-4). s-BuLi/TMEDA reacts with p-anisic acid (3) exclusively in the vicinity of the carboxylate. According to these methodologies, routes to very simple methoxybenzoic acids with a variety of functionalities that are not easily accessible by other means have been developed (Table 1).

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“…Methods for carrying out this transformation include oxidation by using ceric ammonium nitrate (CAN), [16] hypervalent iodine reagents [20] or anodic methods. [21] Initial efforts in this area have been fruitful with the successful CAN oxidation of compound rac-20.…”

Section: Resultsmentioning

confidence: 99%

Towards a Total Synthesis of the New Anticancer Agent Mensacarcin: Synthesis of the Carbocyclic Core

Tietze¹,

Stewart²,

Polomska³

et al. 2004

Chemistry A European J

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A synthesis of the carbocyclic core associated with the new anticancer agent mensacarcin (1) is reported. The strategy involves the synthesis of several novel highly substituted aromatic compounds, such as 12 and 23. The lithium derivative of 12 readily engages in a nucleophilic addition to benzaldehyde 4 to provide the diphenylcarbinol rac-15. The analogous benzyl ether rac-16 undergoes an intramolecular Heck reaction to provide the required tetrahydroanthracene rac-17, which can be transformed into the key tricyclic methyl ether rac-20. In a second approach, the lithium derivative of 21 is added to the hexasubstituted benzaldehyde 23 to give the diphenylcarbinol rac-35. Subsequent methylation to rac-36 followed by an intramolecular Heck reaction provides tricycle rac-37. Similarly, the oxidised compound 40 provides an electronically more suitable intramolecular Heck partner to afford compound 41. Further transformations of these substrates leads to rac-43, which incorporates the core structure of mensacarcin (1).

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New Chiral Pool Approach to Anthracyclinones. The Stereoselective Synthesis of Idarubicinone

Cited by 21 publications

References 23 publications

(1S,3S)-1-tert-Butyldiphenylsiloxy-3-hydroxy-3-isopropenyl-1,2,3,4-tetrahydronaphthalene

(1S,3S)-1-tert-Butyldiphenylsiloxy-3-hydroxy-3-isopropenyl-1,2,3,4-tetrahydronaphthalene

First General, Direct, and Regioselective Synthesis of Substituted Methoxybenzoic Acids by Ortho Metalation

Towards a Total Synthesis of the New Anticancer Agent Mensacarcin: Synthesis of the Carbocyclic Core

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