Synthesis of macrocyclic terpenoids by intramolecular cyclization. XI. Total synthesis of zerumbone.

Starting from ethyl 3-(1-naphthyl)propionate (1), the dibasic acid 4-(4-carboxy-ethyl-I-naphthyl)butyric acid (3) was prepared, which served as a key compound for the synthesis of 5,6-dihydro-4H-benz[de]anthraoene (6) by a double intramolecular cyclization. The monocyolization of the dibasic acid (3) gave rise by a preferential six-membered ring closure, to 3-(1-oxo-1,2,3,4-tetrahydro-9-phenanthryl)propionic acid (7). A partial synthesis of 5,6-dihydro-4H-benz[de]anthracene (6), by succinoylation of perinaphthane followed by usual synthetic steps, is reported as confirmatory evidence of the identity of (6) obtained by double cyclization of the diacid. Some aspects of the orientation of intramolecular acylation are discussed.

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Total Synthesis of Eleuthoside A; Application of Rh-Catalyzed Intramolecular Cyclization of Diazonaphthoquinone

Synlett ◽

10.1055/s-0036-1589118 ◽

2017 ◽

Vol 29 (04) ◽

pp. 457-462 ◽

Cited By ~ 6

Author(s):

Mitsuru Kitamura ◽

Dina Othman ◽

Kota Otsuka ◽

Shuhei Takahashi ◽

Khalid Selim ◽

...

Keyword(s):

Total Synthesis ◽

Intramolecular Cyclization ◽

Cyclization Reaction ◽

Successful Strategy ◽

Separation Of Diastereomers ◽

Metal Catalyzed ◽

Natural Cytotoxic

The first total synthesis of (±)-eleutherol and eleuthoside A, the natural cytotoxic substances extracted from medicinal Indonesian plant, is described. First, the synthesis of (±)-eleutherol has been accomplished in nine steps starting from bromo methoxy aldehyde with the aid of diazo-transfer chemistry approach. Second, a metal-catalyzed intramolecular cyclization reaction of the corresponding diazonaphthoquinone led to the desired eleuotherol, which served as a precursor to eleuthoside A. Then, several glycosidation routes, using different glucosyl donors, were experimented to reach effective O-glycosidation of eleutherol. The only successful strategy involved Koenigs–Knorr glycosidation using peracetyl glycosyl bromide in the presence of Ag2O and quinoline. This strategy furnished our desired acetylated glycoside of β-configuration, regioselectively. Finally, deacetylation and successive separation of diastereomers were conducted to give eleuthoside A.

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Synthesis of macrocyclic terpenoids by intramolecular cyclization IX. Total synthesis of (±)-obscuronatin and (±)-biflora-4,10(19),15-triene.

Tetrahedron Letters ◽

10.1016/s0040-4039(01)81685-3 ◽

1984 ◽

Vol 25 (50) ◽

pp. 5781-5784 ◽

Cited By ~ 18

Author(s):

Mitsuaki Kodama ◽

Kunihito Okumura ◽

Yoshihisa Kobayashi ◽

Tetsuto Tsunoda ◽

Shô Itô

Keyword(s):

Total Synthesis ◽

Intramolecular Cyclization

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ChemInform Abstract: Studies on the Terpenoids and Related Alicyclic Compounds. Part 46. Total Synthesis of (.+-.)-Diplophyllin Using Intramolecular Cyclization of ω-Formyl-β-alkoxycarbonylallylsilane.

ChemInform ◽

10.1002/chin.199526205 ◽

2010 ◽

Vol 26 (26) ◽

pp. no-no

Author(s):

K. NISHITANI ◽

J. SUZUKI ◽

H. ISHIBASHI ◽

Y. SAITOH ◽

S. KARIYA ◽

...

Keyword(s):

Total Synthesis ◽

Intramolecular Cyclization

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Total Synthesis of Bouchardatine

Australian Journal of Chemistry ◽

10.1071/ch13331 ◽

2013 ◽

Vol 66 (9) ◽

pp. 1112 ◽

Cited By ~ 8

Author(s):

Nilesh H. Naik ◽

Tukaram D. Urmode ◽

Arun K. Sikder ◽

Radhika S. Kusurkar

Keyword(s):

Total Synthesis ◽

Intramolecular Cyclization ◽

Type Reaction ◽

Naturally Occurring

Two new, efficient and simple routes using Heck-type reaction and intramolecular cyclization were developed for the synthesis of the naturally occurring cytotoxic alkaloid 2-(4-oxo-3,4-dihydroquinazolin-2-yl)-1H-indole-3-carbaldehyde (bouchardatine).

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Intramolecular Cyclization of Allylsilyl Substituted N-Acyliminium Ions. Access to 1- and 2-Azabicyclo[X.Y.0]alkanes. Total Synthesis of (±)-Mesembrine

Heterocycles ◽

10.3987/com-91-5810 ◽

1992 ◽

Vol 34 (1) ◽

pp. 37 ◽

Cited By ~ 13

Author(s):

Roland Remuson ◽

Yvonne Gelas-Mialhe ◽

Jean-Claude Gramain ◽

Hassane Hajouji ◽

Roland Remuson

Keyword(s):

Total Synthesis ◽

Intramolecular Cyclization ◽

Acyliminium Ions

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Total synthesis of coronafacic acid through 6-endo-trig mode intramolecular cyclization of an enone-aldehyde to a hydrindanone using samarium(II) iodide

Tetrahedron Letters ◽

10.1016/s0040-4039(00)00786-3 ◽

2000 ◽

Vol 41 (26) ◽

pp. 5115-5118 ◽

Cited By ~ 20

Author(s):

Masakazu Sono ◽

Atsuko Hashimoto ◽

Katsuyuki Nakashima ◽

Motoo Tori

Keyword(s):

Total Synthesis ◽

Intramolecular Cyclization ◽

Coronafacic Acid

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Total synthesis, stereochemistry, and lithium–ammonia reduction of (±)-4-demethylaristolone and (±)-5-epi-4-demethylaristolone

Canadian Journal of Chemistry ◽

10.1139/v69-713 ◽

1969 ◽

Vol 47 (23) ◽

pp. 4299-4306 ◽

Cited By ~ 11

Author(s):

Edward Piers ◽

William de Waal ◽

Ronald W. Britton

Keyword(s):

Total Synthesis ◽

Intramolecular Cyclization ◽

Similar Reduction ◽

Dihydro Derivative

The total synthesis of (±)-4-demethylaristolone (14) and its epimer, (±)-5-epi-4-demethylaristolone (15) is described. The key step of this synthesis involves the intramolecular cyclization of the olefinic diazoketone 12, which produces the two epimers, 14 and 15, in a ratio of approximately 2:1, respectively. The stereochemistry of the two epimers is unambiguously determined. It is observed that the lithium–ammonia reduction of 14 gives a dihydro derivative 16 containing trans-fused six-membered rings, while, interestingly, a similar reduction of 15 affords the corresponding cis-fused decalone system 26.

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