Alkaloid Studies. VIII.<sup>1</sup> The Structures of the Diterpenoid Alkaloids Laurifoline and Cuauchichicine

Djerassi, Carl; Smith, Craig R.; Lippman, A. E.; Figdor, S. K.; Herrán, José Manuel González

doi:10.1021/ja01623a033

Cited by 32 publications

(9 citation statements)

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“…In 1955, the diterpenoid alkaloid garryfoline (1) was reported to rearrange rapidly to cuauchichicine (2) in dilute mineral acid at room temperature. 1 A similar rearrangement has been observed in other diterpenoid alkaloids, e.g., atisine, kobusine, and napelline. 2 In contrast to the rapid rearrangement of garryfoline, the 15-epimeric veatchine (3) is stable even on heating in dilute hydrochloric acid.…”

supporting

confidence: 59%

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Study of the Acid-Catalyzed Isomerization of Dihydroveatchine

Bai

Pelletier

1997

J. Nat. Prod.

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A study of the acid-catalyzed isomerization of dihydroveatchine (5) resulted in the isolation of a single major compound, the aldehyde 6. Structure 6 has been derived from its spectral data. Reduction of 6 with NaBH4 gave compound 7, which was characterized through detailed NMR studies including 1D, 2D, and selective INEPT experiments, as well as preparation of its mono- and bis(p-nitrobenzoyl) derivatives 8 and 9. A plausible mechanism for the formation of 6, derived from the spectral data of the isomerized product obtained by deuterium labeling, is reported. Interestingly, the acid-catalyzed isomerization products of the allylic alcohols garryfoline (1) and dihydroveatchine (5) are different and appear to be dependent on the configurational orientation of the C(15) hydroxyl group. Unambiguous NMR chemical shift assignments for 5 are also reported.

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supporting

confidence: 59%

“…In 1955, the diterpenoid alkaloid garryfoline ( 1 ) was reported to rearrange rapidly to cuauchichicine ( 2 ) in dilute mineral acid at room temperature . A similar rearrangement has been observed in other diterpenoid alkaloids, e.g., atisine, kobusine, and napelline …”

mentioning

confidence: 70%

Study of the Acid-Catalyzed Isomerization of Dihydroveatchine

Bai

Pelletier

1997

J. Nat. Prod.

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“…This type of acid‐catalysed rearrangement of allylic alcohol to the corresponding saturated ketone has been previously reported. [2f], …”

Section: Resultsmentioning

confidence: 99%

Hetero‐Diels–Alder and Ring‐Opening Reactions of Furans Applied to the Synthesis of Functionalized Heterocycles

et al. 2017

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Furans have been explored as a scaffold for the synthesis of a range of heterocyclic compounds, exploring their dienophilic behaviour towards nitroso‐ and azoalkenes as the first step. Acid‐catalysed rearrangements of these cycloadducts, 4a,7a‐dihydro‐4H‐furo[2,3‐e][1,2]oxazines and 1,4,4a,7a‐tetrahydrofuro[3,2‐c]pyridazines, were studied. Using 1 equiv. of TFA, the bicyclic heterocycles derived from furan and 2‐methylfuran were converted into furans bearing side‐chains incorporating oxime and hydrazone groups by ring‐opening of the six‐membered ring with the concomitant aromatization of the furan ring. The use of TFA as solvent led to rearrangement via spirocyclic intermediates, followed by furan ring‐opening to afford functionalized isoxazoles or pyrazoles. Furthermore, furo‐oxazines derived from 2,5‐dimethylfuran, in which furan aromatization is precluded, were converted efficiently into 6H‐1,2‐oxazines through a furan ring‐opening reaction upon thermolysis in the presence of a catalytic amount of p‐toluenesulfonic acid. The tetrahydrofuro[3,2‐c]pyridazines derived from furan and dimethylfuran underwent acid‐catalysed addition reactions, leading to 6‐substituted hexahydrofuro[3,2‐c]pyridazines, when in the presence of alcohols or water.

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“…130-133°C., [a]D = -60°, and cuauchichicine, C22H33NO2, m.p. 152-155°C., [a]D = -71.4°, were isolated from Garrya laurifolia Hartw., a Mexican tree commonly known as "cuauchichic" (53,54). Garryfoline is isomerized to cuauchichicine by acid.…”

Section: Cooh Cooh C Garryine and Veatchinementioning

confidence: 99%

Diterpenoids

Tsutsui¹,

Tsutsui²

1959

Chem. Rev.

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Alkaloid Studies. VIII.¹ The Structures of the Diterpenoid Alkaloids Laurifoline and Cuauchichicine

Cited by 32 publications

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Study of the Acid-Catalyzed Isomerization of Dihydroveatchine

Study of the Acid-Catalyzed Isomerization of Dihydroveatchine

Hetero‐Diels–Alder and Ring‐Opening Reactions of Furans Applied to the Synthesis of Functionalized Heterocycles

Diterpenoids

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Alkaloid Studies. VIII.1 The Structures of the Diterpenoid Alkaloids Laurifoline and Cuauchichicine

Cited by 32 publications

References 0 publications

Study of the Acid-Catalyzed Isomerization of Dihydroveatchine

Study of the Acid-Catalyzed Isomerization of Dihydroveatchine

Hetero‐Diels–Alder and Ring‐Opening Reactions of Furans Applied to the Synthesis of Functionalized Heterocycles

Diterpenoids

Contact Info

Product

Resources

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Alkaloid Studies. VIII.¹ The Structures of the Diterpenoid Alkaloids Laurifoline and Cuauchichicine