(+)-Podocarpic Acid as Chiral Template in the Synthesis of Aphidicolane, Stemodane and Stemarane Diterpenoids †.
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.
Dipartimento di Chimica, Università degli Studi di Roma "La Sapienza", P.le Aldo Moro, 5, I-00185 Roma, Italy. angela.labella@uniroma1.it.
Angela
A
La Bella
Dipartimento di Biologia Ambientale, Università degli Studi di Roma "La Sapienza", P.le Aldo Moro, 5, I-00185 Roma, Italy. francesca.leonelli@uniroma1.it.
Francesca
F
Leonelli
Dipartimento di Chimica, Università degli Studi di Roma "La Sapienza", P.le Aldo Moro, 5, I-00185 Roma, Italy. luisamaria.migneco@uniroma1.it.
Luisa Maria
LM
Migneco
Dipartimento di Chimica, Università degli Studi di Roma "La Sapienza", P.le Aldo Moro, 5, I-00185 Roma, Italy. rinaldo.marinibettolo@uniroma1.it.
Rinaldo
R
Marini Bettolo
D045784:Abietanes / Q000138:chemical synthesis* / Q000737:chemistry*; D000068543:Calceolariaceae / Q000737:chemistry*; D000068377:Plantaginaceae / Q000737:chemistry*
D045784:Abietanes; C002470:podocarpic acid
aphidicolin; podocarpic acid; stemarin; stemodin; synthesis