Total synthesis of the stemodane-type diterpenoids, (±)-2-desoxystemodinone, (+)-2-desoxystemodinone, and (±)-stemodinol

Kelly, Robert C.; Harley, Mary Lou; Alward, Sandra J.; Rej, Rabindra; Gowda, G. Byre; Mukhopadhyay, Asish K.; Manchand, Percy S.

doi:10.1139/v83-048

Cited by 29 publications

(30 citation statements)

References 3 publications

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“…Reduction of the latter with tri-n-butyltin hydride followed by saponification gave 47. The conversion of 47 into (+)-36 [51] paralleled that of 42a into (+)-31 [50] (see Section 8.4). …”

Section: Synthesis Of (+)-Aphidicol-15-ene (1984)mentioning

confidence: 92%

“…In the following years the Kelly group focused its attention on stemodane and aphidicolane diterpenoids. In this frame the syntheses of (+)-stemod-12-ene (31), (+)-2-deoxystemodinone (2d) [50] and (+)-aphidicol-15-ene (36) [51] from (+)-podocarpic acid (4) were achieved.…”

Section: Synthesis Of 17-norstemodan-16-one (1982)mentioning

confidence: 99%

“…The alcohol 42a was then transformed into the corresponding tosylate 34 which on heating in DMSO in the presence of the methyl sulfinyl carbanion gave (+)-stemod-12-ene (31) (see Section 8.3). (+)-2-Deoxystemodinone (2d) was eventually obtained from (+)-31 by epoxidation followed by hydride epoxide reduction [50]. The use of (+)-podocarpic acid (4) as starting material also allowed confirmation of the absolute configuration attributed to the stemodane diterpenoids on the basis of ORD and CD studies.…”

Section: Synthesis Of (+)-Stemod-12-ene and (+)-2-deoxystemodinone (1mentioning

confidence: 99%

“…Compound (+)-53, whose relative configuration was confirmed by an X-ray structure determination, was then stereoselectively epoxidized to (+)-54. The epoxidation of the stemod-12-ene system proceeds, in fact, from the less hindered α face [50]. Reduction of (+)-54 with LiAlH 4 gave then the diol 2e which was then acetylated to (+)-2f [53].…”

Section: Proof Of the Structure Of The Stemodia Chilensis Tetracyclicmentioning

confidence: 99%

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(+)-Podocarpic Acid as Chiral Template in the Synthesis of Aphidicolane, Stemodane and Stemarane Diterpenoids †

et al. 2016

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Abstract:In this review the synthetic work in the field of aphidicolane, stemodane and stemarane diterpenoids, in which readily available (+)-podocarpic acid (4) was used as chiral template for the construction of their polycyclic structures, is described as it developed along the years. In the frame of this work (+)-podocarpic acid (4) was a very useful tool in a model study leading to the syntheses of tetracyclic ketones 7 and 8, models of key intermediates 5a and 6 in the syntheses of (+)-aphidicolin (1) and (+)-stemodin (2a), respectively. (+)-Podocarpic acid (4) was also converted into (+)-2-deoxystemodinone (2d), allowing confirmation of the stemodane diterpenoids absolute configuration, into (+)-aphidicol-15-ene (36) and into Stemodia chilensis tetracyclic diterpenoid (+)-19-acetoxystemodan-12-ol (2f), allowing confirmation of its structure. (+)-Podocarpic acid (4) was then extensively used in the work which led to the synthesis of (+)-stemar-13-ene (57) and (+)-18-deoxystemarin (3b). Finally, (+)-4 was converted into (+)-2-deoxyoryzalexin S (66), which made it possible to demonstrate that the structure of (+)-66 could not be attributed to a Chilean Calceolaria isolated diterpenoid to which this structure had been assigned.

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“…Reduction of the latter with tri-n-butyltin hydride followed by saponification gave 47. The conversion of 47 into (+)-36 [51] paralleled that of 42a into (+)-31 [50] (see Section 8.4). …”

Section: Synthesis Of (+)-Aphidicol-15-ene (1984)mentioning

confidence: 92%

Section: Synthesis Of 17-norstemodan-16-one (1982)mentioning

confidence: 99%

Section: Synthesis Of (+)-Stemod-12-ene and (+)-2-deoxystemodinone (1mentioning

confidence: 99%

Section: Proof Of the Structure Of The Stemodia Chilensis Tetracyclicmentioning

confidence: 99%

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(+)-Podocarpic Acid as Chiral Template in the Synthesis of Aphidicolane, Stemodane and Stemarane Diterpenoids †

et al. 2016

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“…This intermediate, prepared from podocarpic acid (3), is the enantiomer represented by 6 and leads to the enantiomer 5 derived from aphidicolin (4).…”

Section: -Hydroxybicyclo[222]octan-2-one System Represented Bymentioning

confidence: 99%

A synthesis of (+)-aphidicol-15-ene

Kelly¹,

Lal²,

Gowda³

et al. 1984

Can. J. Chem.

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A stereospecific synthesis of (+)-aphidicol-15-ene is described. Pursuing a concept successfully applied to our total synthesis of stemarin and the stemodane diterpenoids, the C/D ring system was elaborated by functional group manipulation and rearrangement of a 6-hydroxybicyclo[2.2.2]octan-2-one system. RONALD B. KELLY, G. SANKAR LAL, GOPALA GOWDA et RABINDRA N. Rw. Can. J. Chem. 62, 1930Chem. 62, (1984. This concept was an efficient feature of total syntheses of stemarin (1)(1), and of 2-desoxystemodinone (2a) and stemodinol (2b)(2,3); we now wish to describe its application to a stereospecific synthesis of (+)-aphidicol-15-ene (5), a derivative of aphidicolin (3)(4).' This synthesis was undertaken as a model, relative to a projected total synthesis of aphidicolin.The keto alcohol 6, formerly encountered as an intermediate in our synthesis of (+)-2-desoxystemodinone (2a)(3), served also as an intermediate in the present synthesis. This intermediate, prepared from podocarpic acid (3), is the enantiomer represented by 6 and leads to the enantiomer 5 derived from aphidicolin (4).In preparation for the rearrangement of the bicyclic system of 6 to that of 5, it was necessary to reduce the secondary hydroxyl group to a methylene group and convert the keto

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The Total Synthesis of Tri‐ and Tetracyclic Diterpenes

Goldsmith

1991

Total Synthesis of Natural Products

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Total synthesis of the stemodane-type diterpenoids, (±)-2-desoxystemodinone, (+)-2-desoxystemodinone, and (±)-stemodinol

Cited by 29 publications

References 3 publications

(+)-Podocarpic Acid as Chiral Template in the Synthesis of Aphidicolane, Stemodane and Stemarane Diterpenoids †

(+)-Podocarpic Acid as Chiral Template in the Synthesis of Aphidicolane, Stemodane and Stemarane Diterpenoids †

A synthesis of (+)-aphidicol-15-ene

The Total Synthesis of Tri‐ and Tetracyclic Diterpenes

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