Two New Diterpenes from Stemodia maritima L.

Hufford, Charles D.; Guerrero, Ricardo O; Doorenbos, Norman J.

doi:10.1002/jps.2600650550

Cited by 38 publications

(50 citation statements)

References 3 publications

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“…(+)-Stemodin (2a) was isolated in 1973, along with (+)-stemodinone (2b), from Stemodia maritima L. [3]. In 1975 (+)-stemarin (3a) [4] and stemodane diterpenoid maritimol (2c) [5] were also isolated from the same plant. The number of isolated diterpenoids of these classes grew in the following years.…”

Section: Aphidicolane Stemodane and Stemarane Diterpenoidsmentioning

confidence: 99%

(+)-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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Section: Aphidicolane Stemodane and Stemarane Diterpenoidsmentioning

confidence: 99%

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

et al. 2016

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“…After 30 min, a solution of the allylic alcohol 10 (3.00 g, 16.3 mmol) in dry CH 2 Cl 2 (3 ml) was added dropwise to the mixture at Ϫ20°C, and the mixture was stirred for 4 h at Ϫ20°C. To the mixture were successively added water at 0°C and 30% NaOH/saturated NaCl, and the mixture was stirred vigorously at room temperature for 2 h. The organic phase was filtered through Celite and dried over MgSO 4 . Concentration under reduced pressure gave a residual oil, which was purified by column chromatography over silica gel (n-hexane : EtOAcϭ1 : 2) to afford the epoxide 11 (2.67 (S)-2-(Methoxymethoxymethyl)-1-oxaspiro[2.5]octan-6-one 6,6-Ethylene Acetal (12) To a stirred solution of 11 (1.00 g, 5.00 mmol) in dry CH 2 Cl 2 (13 ml) were added (i-Pr) 2 NEt (1.80 ml, 1.00 mmol) and MOMCl (0.75 ml, 10.0 mmol), and the mixture was stirred overnight at room temperature.…”

Section: (S)-2-(hydroxymethyl)-1-oxaspiro[25]octan-6-one 66-ethylenmentioning

confidence: 99%

“…The resulting white precipitate was filtered off, and the filtrate was extracted with Et 2 O. The extract was washed with 2 N NaOH, water, and brine, and dried over MgSO 4 . Concentration under reduced pressure gave a residual oil, which was purified by column chromatography over silica gel (nhexane : EtOAcϭ5 : 1) to afford the alcohol 13 ( -4-(prop-2-enyl)cyclohexan-1-one 1,1-Ethylene Acetal (14a) To a stirred solution of 13 (8.0 mg, 0.030 mmol) in dry CH 2 Cl 2 (0.3 ml) were successively added Et 3 N (8.3 ml, 0.059 mmol), 4-dimethylaminopyridine (DMAP; 3.3 mg, 0.030 mmol), and (ϩ)-MTPACl (7.9 ml, 0.045 mmol), and the mixture was stirred for 30 min at room temperature.…”

Section: -[(R)-1-hydroxy-2-(methoxymethoxy)ethyl]-4-(prop-2-enyl)cycmentioning

confidence: 99%

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Construction of Tricyclic Enone, a Common Precursor for Aphidicolane and Stemodane B/C/D-Ring System

Tanaka

Yamamoto

Hiramatsu

et al. 2006

CHEMICAL & PHARMACEUTICAL BULLETIN

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The leaves of the rare littoral plant, Stemodia maritima L. (fam. Scrophulariaceae), from Jamaica have long been used as a folk medicine for the treatment of venereal disease in the Caribbean Islands.1) Attracted by the reported medicinal properties, Manchand and others isolated and characterized structurally unique tetracyclic diterpenes, stemodin 1 and stemodinone 2 (Fig. 1).2-7) Aphidicolin (3), 8,9) which has a highly related tetracyclic ring system to stemodanes 1 and 2, was isolated from Cephalalosporium aphidicola by Hesp and co-workers and later found to occur in Nigrosporum sphaerica. The fusion of the five-membered C ring to B in stemodanes 1 and 2 is cis in contrast to the trans fusion in aphidicolin 3. Aphidicolin is known as a potent antitumor (inhibits DNA replication and growth of several human and neoplastic cells) [10][11][12] and antiviral agent (promising activity against Herpes simplex).13-15) Stemodanes, with a similar structure to aphidicolanes, is expected to have related pharmacological activities.Their important medicinal properties as well as the presence of more than six stereocenters and four quaternary carbons, especially the two adjacent quaternary carbons at C-9 and C-10, make these natural products a worthy synthetic challenge.16) Although there are several reports on the synthesis of stemodinone, [17][18][19][20] other stemodanes, [21][22][23][24][25][26][27][28][29][30][31][32][33] and aphidicolanes [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53] in a racemic form, asymmetric synthesis of this class of compounds is relatively rare.54-58) The asymmetric total synthesis of aphidicolin was first achieved by Holton and co-workers in 1987. 54) After that, formal synthesis of (ϩ)-aphidicolin was reported by Tanis 55) and Fukumoto.56) Recently, total synthesis of aphidicolanes using transannular Diels-Alder reaction was achieved by Deslongchamps and co-workers.57,58) These synthetic routes are extremely important in that the complex tetracyclic skeleton was constructed in an enantioenriched form; however, they are limited to the synthesis of a single aphidicolane or stemodane diterpene. Synthesis of other natural products or their analogs is not easily accessible by these routes because in many cases the A-ring having oxygen functionalities was constructed at the earlier stage of the synthetic routes. Therefore, development of a systematic synthetic route leading to various kinds of aphidicolanes, stemodanes, and their analogs in an enantiomerically pure form is desirable.We then planned a novel flexible synthetic route which can be applied to the synthesis of a variety of aphidicolanes and stemodanes, based on the asymmetric construction of the B/C/D ring system followed by formation of the highly-functionalized A-ring. A tricyclic enone 4 is considered as the key intermediate, which would lead to either natural or nonnatural aphidicolanes and stemodanes by stereoselective hydrogenation of the double bond as shown in Chart 1. In this paper, we descri...

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“…The asymmetric total synthesis of (ϩ)-maritimol (23), reported in 2000 by Deslongchamps and colleagues (13), utilizes a transannular Diels-Alder reaction to install the adjacent quaternary carbons present in this stemodane diterpenoid (14,15). Their strategy is briefly outlined in Scheme 4.…”

mentioning

confidence: 99%

Contiguous stereogenic quaternary carbons: A daunting challenge in natural products synthesis

Peterson

Overman

2004

Proc. Natl. Acad. Sci. U.S.A.

353

119

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Two New Diterpenes from Stemodia maritima L.

Cited by 38 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 †

Construction of Tricyclic Enone, a Common Precursor for Aphidicolane and Stemodane B/C/D-Ring System

Contiguous stereogenic quaternary carbons: A daunting challenge in natural products synthesis

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