Syntheses in the series op lycopodiom alkaloids IV. A simple photochemical synthesis of an annotinine derivative

Wiesner, K.; Jirkovsky, Ivo; Fishman, Mikkel; Williams, Christian A.

doi:10.1016/s0040-4039(00)90993-6

Cited by 21 publications

(4 citation statements)

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“…Found: C, 54.02; , 5.70; N, 3.47. Preparation of 3-Methoxy-l,3,5(10),13-tetraene-8-azagonan-17-one (9b). A stirred suspension of 0.50 g (1.34 mmol) of 3methoxy-l,3,5 (10),8 (14),13(17)-pentaene-8-azagonan-17-ol perchlorate (8b) in 30 ml of methylene chloride was treated with 10 ml of 5% aqueous sodium hydroxide as in the preparation of 9a to give 0.30 g (82.4%) of 3-methoxyl-l,3,5(10),13-tetraene-8-azagonan-17one (9b): mp 122-125°; pmr (CDCLt) 4.67 (m, 1 ), 3.90 azagonan-17-one (13). A solution of 1.0 g (3.3 mmol) of 2,3-dimethoxy-l,3,5(10),13-tetraene-8-azagonan-17-one (9a) dissolved in 80 ml of dry tetrahydrofuran was treated with 0.25 g of lithium aluminum hydride and was heated under reflux for 3 hr.…”

Section: Methodsmentioning

confidence: 99%

“…The appearance of Bohlmann bands at 2810 and 2890 cm-1 in the infrared spectrum24 and the comparison of the pmr spectrum with related aza steroids25 allowed the assignment of the trans-anti-cis stereochemistry to the product, 2,3-dimethoxy-l,3,5(10)-triene-8-azagonan-17-one (13).26…”

mentioning

confidence: 99%

“…No C-alkylated product was detected. Attempts to cause a Claisen-type rearrangement of the vinyl allyl ether27 by heating 19 gave only the dealkylated product 13.…”

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confidence: 99%

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Novel synthesis of 8-Aza Steroids

Lyle¹,

Heavner²

1975

J. Org. Chem.

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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Novel synthesis of 8-Aza Steroids

Lyle¹,

Heavner²

1975

J. Org. Chem.

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“…The same research group that reported the total synthesis of the Lycopodium alkaloid annotinine (284) in 1967 [212][213][214][215] deduced the structure of the molecule during the years 1956-1957 (Scheme 52). 216 Their synthesis starts with a condensation of acrylic acid and vinylogous amide 281 to provide the [2C2] photochemical cycloaddition substrate 282.…”

Section: Annotininementioning

confidence: 99%

Synthesis of propellane-containing natural products

2005

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Enone Olefin [2 + 2] Photochemical Cycloadditions

Crimmins

Reinhold

1993

Organic Reactions

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The photochemical [2 + 2] cycloaddition reaction of alkenes to enones, the light‐induced cycloaddition of an excited state enone to a ground state alkene to produce a cyclobutane, is a highly useful reaction in organic synthesis since two new carbon–carbon bonds are formed and a maximum of four new stereogenic centers are introduced into the molecule in the process. The first [2 + 2] photocycloaddition reaction was reported by Ciamician in 1908 when he observed the formation of carvone camphor on exposure of carvone to sunlight for one year. After confirmation of this finding in the late 1950s numerous investigators immediately recognized the value of the reaction for the rapid construction of complex molecular frameworks. The photocycloaddition of a series of Diels–Alder adducts of various dienes and benzoquinones to efficiently produce complex caged structures was subsequently carried out. This included the cycloaddition of a diketone to form a diketone. Meanwhile, a similar photochemical cycloaddition of an enone was utilized in a synthesis of the platonic solid cubane. Shortly thereafter investigations of the intermolecular reaction were initiated through a study of the dimerization of cyclopentenone and the photocycloaddition of cyclopentenone to cyclopentene. Further investigation of the various synthetic and mechanistic aspects of the photocycloaddition resulted in several total syntheses, including caryophyllene and bourbonene, as well as a proposed mechanistic rationale for the reaction. As a result of this pioneering work, largely by Eaton, Corey, and De Mayo, numerous natural and nonnatural products have been prepared by synthetic routes which have a [2 + 2] photocycloaddition as a crucial step in their synthesis. Through further refining over the last 15–20 years, the photocycloaddition reaction has become recognized as an important transformation in the repertoire of the synthetic organic chemist. Both the intermolecular and intramolecular versions of the reaction have been extensively studied. The intramolecular photocycloaddition, like the intramolecular variation of many reactions, has been the subject of much recent work. It is generally thought to be more predictable with regard to regiochemical and stereochemical control, but as will be seen from many of the examples in this chapter, the intermolecular reaction can be highly selective and predictable if the proper reaction participants and conditions are chosen. This chapter reviews the literature on the enone olefin [2 + 2] photocycloaddition since its discovery. Because of the volume of work in the field, there will undoubtedly be some omissions. Examples of all the major types of enone alkene photocycloadditions have been included so that the reader can get a sense of the historical evolution and the current state of the art. Both the inter molecular and the intra molecular variants of this reaction are treated in this chapter. The reader is also referred to a number of excellent reviews on the inter molecular reaction, the intra molecular reaction, and complete treatments which have appeared.

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Syntheses in the series op lycopodiom alkaloids IV. A simple photochemical synthesis of an annotinine derivative

Cited by 21 publications

References 4 publications

Novel synthesis of 8-Aza Steroids

Novel synthesis of 8-Aza Steroids

Synthesis of propellane-containing natural products

Enone Olefin [2 + 2] Photochemical Cycloadditions

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