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
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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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