Notably Enhanced Reactivity of the Fulleroid anti-Bredt Double Bond in Diels-Alder Reactions

2011 ◽  
Vol 2011 (32) ◽  
pp. 6452-6458 ◽  
Author(s):  
Naohiko Ikuma ◽  
Yasunori Susami ◽  
Takumi Oshima
Keyword(s):  
Double Bond ◽  
Diels Alder

scholarly journals Stereoselective total syntheses of (±)-sinularene and (±)-5-epi-sinularene: a general intramolecular Diels–Alder approach to tricyclic sesquiterpenes

1985 ◽  
Vol 63 (4) ◽  
pp. 993-995 ◽  
Author(s):  
Kazimierz Antczak ◽  
John F. Kingston ◽  
Alex G. Fallis
Keyword(s):  
Double Bond ◽  
Methyl Ester ◽  
Total Synthesis ◽  
Ring System ◽  
Diels Alder ◽  
Exocyclic Double Bond ◽  
Total Syntheses ◽  
Methyl Group ◽  
Secondary Hydroxyl ◽  
Selective Hydrogenolysis

Stereoselective total synthesis of (±)-sinularene and (±)-5-epi-sinularene are described. The sequence employs a "blocked" cyclopentadiene in which the cyclopropane unit also serves as a latent methyl group. Thus intramolecular [4 + 2] cycloaddition of the substituted methyl spiro[2.4]hepta-4,6-dien-1-yl)-2-pentenoate 11 affords 5-benzyloxy-6-isopropyl-8-carbomethoxytetracyclo[5.4.01,7.02,4.02,9]undec-10-ene (12) which after selective hydrogenolysis generates the tricyclo[4.4.01,6.02,8]decane (sinularene) ring system. Removal of the secondary hydroxyl function (Ph3P/CCl4/CH3CN; H2/Pd/C), reduction of the methyl ester (LiAlH4), and introduction of the exocyclic double bond (acetate pyrolysis, 550 °C) completes the synthesis of (±)-sinularene in 14 steps from cyclopentadiene. A parallel series of reactions employing the isopropyl epimer of 12 affords (±)-5-epi-sinularene.

scholarly journals Zur Reaktivität des Germaethens Me2Ge=C(SiMe3)2: Mechanistische Aspekte der Diels-Aider- und En-Reaktionen [1] / On the Reactivity of Germaethene Me2Ge=C (SiMe3)2: Mechanistic Aspects of Diels Alder and Ene Reactions [1]

1996 ◽  
Vol 51 (6) ◽  
pp. 838-850 ◽  
Author(s):  
Nils Wiberg ◽  
Susanne Wagner
Keyword(s):  
Double Bond ◽  
Energy Difference ◽  
Diels Alder ◽  
Bond Polarity ◽  
Ene Reactions ◽  
Ene Reaction

Abstract Diels-Alder and ene reactions of germaethene Me2Ge=C(SiMe3)2 (2) with butadienes respectively, take place regioselectively, as well as stereoselectively. They are accelerated by an increasing tendency of substituents in butadiene or propene to donate electrons (e.g. 2-methylbutadiene > butadiene; 2-methylpropene > propene), and retarded by an increasing bulkyness of substituents in 1,4- or 1,3-positions (e.g. 1-methylbutadiene > 2-methylbutadiene; 1-vinylpropene > propene). It is concluded from these studies that Diels-Alder and ene reactions of 2 occur - like those of Me2Si=C(SiMe3)2 (1) or of ethenes >C=C< - in a concerted way and are HOMOdiene-LUMOdienophile and HOMOene-LUMOenophile controlled. Thus 2 and 1 behave as carbon analogues. With regard to a specific diene or ene (e.g. anthracene; toluene), 2 is the better dienophile or enophile than 1 or ethenes. With a fixed diene/ene mixture (e.g. butadiene/propene), 2 acts as the better dienophile, while 1 is the better enophile. These results can be explained by the π/π*- energy difference and the double bond polarity decreasing in the direction 1 > 2. Only cis-piperylene gives a [2+2] cycloadduct with 2. besides two [4+2] cycloadducts, and an ene reaction product

Exploratory synthetic investigations related to 12a-deoxypillaromycinone

2002 ◽  
Vol 80 (6) ◽  
pp. 728-738 ◽  
Author(s):  
Lan Wang ◽  
Sanath K Meegalla ◽  
Cheng-Lin Fang ◽  
Nicholas Taylor ◽  
Russell Rodrigo
Keyword(s):  
Double Bond ◽  
Catalytic Hydrogenation ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction ◽  
Step Procedure ◽  
Key Steps

Furfural is converted to suitably substituted AB synthon 21 for 12a-deoxypillaromycinone in 10 steps by a sequence involving the following key steps: intramolecular Diels-Alder reaction of a furan, 5-endo-trig cleavage of the oxabicyclo adducts 18, and catalytic hydrogenation of the double bond of a tetrasubstituted enone to produce 19. Enones 21a and 21b obtained by dehydrogenation of 19a and 19b, respectively, are then annulated with ethyl 2-methoxy-6-methylbenzoate in a four-step procedure to generate tetracyclic products 25 in 14 steps from furfural.

Unexpected Variations in the Reactivities and Selectivities of Acyclic and Cyclic Dehydrodipeptides in Diels-Alder Reactions

1998 ◽  
Vol 51 (11) ◽  
pp. 993 ◽  
Author(s):  
Brendan A. Burkett ◽  
Christina L. L. Chai ◽  
David C. R. Hockless
Keyword(s):  
Double Bond ◽  
Diels Alder

Author to whom correspondence should be addressed. The Diels-Alder reactions of some acyclic and cyclic dehydrodipeptides have been investigated. Our studies show that the reactivities of the dehydrodipeptides are sensitive to the environment of the double bond. In addition, theexo / endo selectivity of the cycloaddition is enhanced in the cyclic as compared to the acyclic systems.

Diels-alder reactions of 1-sulfinyldienes with an endocyclic double bond: The unexpected evolution of the n-methylmaleimide adducts.

1994 ◽  
Vol 5 (8) ◽  
pp. 1439-1442 ◽  
Author(s):  
M.Carmen Carreño ◽  
M.Belén Cid ◽  
Françoise Colobert ◽  
José L. Garcia^Ruano ◽  
Guy Solladié
Keyword(s):  
Double Bond ◽  
Diels Alder

Model Compounds Related to Saquayamycin. Attempts to Oxygenate the A/B Ring Junction

2002 ◽  
Vol 55 (5) ◽  
pp. 343 ◽  
Author(s):  
M. A. Apponyi ◽  
J. H. Bowie ◽  
B. W. Skelton ◽  
A. H. White
Keyword(s):  
Double Bond ◽  
Maleic Anhydride ◽  
Good Yield ◽  
Ring Opening ◽  
Diels Alder ◽  
Aromatic System ◽  
Model Compounds ◽  
Similar Treatment ◽  
Ring Junction

The aim of this project was to attempt to find a method for introducing the cis-dihydroxyl substitution at the A/B-ring junction of model compounds related to the saquayamycins. The Diels-Alder reactions of maleic anhydride and bromomaleic anhydride with 5,5-dimethyl-3-vinylcyclohexa-1,2-dienyl acetate gave the two required endo-adducts in good yield, namely (octahydrobenzo[e]isobenzofuran-9-yl acetate (6) and (octahydrobenzo[e]isobenzofuran-9-yl acetate (9). Each of these was converted into the B-ring mono-epoxide, namely (H-benzo[e]oxireno-2,3-furan-1-yl acetate (7) and a mixture of two racemic diastereoisomers of 9a-bromo-3,3-dimethyl-7,9-dioxoperhydrobenzo[e]oxi- reno[2,3-f]isobenzofuran-1-yl acetate (12), respectively. It was then hoped to deprotonate both (7) and (12) at the 9a position in order to effect migration of the 8,9 double bond to the 9,9a position. Reaction of (7) with a mild base (pyridine) did not effect any reaction. Similar treatment of (12) did remove the 9a proton, but it also effected ring opening of the epoxide, followed by dehydration and dehydrobromination to give an excellent (but unwanted) yield of the aromatized system (±)-7,7-dimethyl-1,3-dioxo-1,3,5,7-tetrahydrobenzo (e]isobenzofuran-9-yl acetate. Dehydrobromination of (9), and deprotonation of the 9a position, similarly formed the aromatic system (e]isobenzofuran-9-yl acetate (11) in good yield.

A general intramolecular Diels–Alder approach to tricyclic sesquiterpenes: stereoselective total syntheses of (±)-sinularene and (±)-5-epi-sinularene

1987 ◽  
Vol 65 (1) ◽  
pp. 114-123 ◽  
Author(s):  
Kazimierz Antczak ◽  
John F. Kingston ◽  
Alex G. Fallis ◽  
Alfred W. Hanson
Keyword(s):  
Double Bond ◽  
Methyl Ester ◽  
Ring System ◽  
Diels Alder ◽  
Exocyclic Double Bond ◽  
Total Syntheses ◽  
Methyl Group ◽  
X Ray ◽  
12 Steps ◽  
Selective Hydrogenolysis

Stereoselective total syntheses of (±)-sinularene and (±)-5-epi-sinularene are described. The sequence employs a "blocked" cyclopentadiene in which the cyclopropane unit also serves as a latent methyl group. Thus intramolecular [4 + 2] cycloaddition of the substituted methyl spiro[2.4]hepta-4,6-dien-1-yl-2-pentenoate 13c affords 5-benzyloxy-6-isopropyl-8-carbomethoxytetracyclo[5.4.01,7.02,4.02,9]undec-10-ene (14c), which after selective hydrogenolysis generates the tricyclo[4.4.01,6.02,8]decane (sinularene) ring system. Removal of the secondary hydroxyl function by elimination and hydrogenation (Ph3P/CCl4/CH3CN; H2/Pd/C), reduction of the methyl ester (LiAlH4), and introduction of the exocyclic double bond (acetate pyrolysis, 550 °C) completes the synthesis of (±)-sinularene in 12 steps from aldehyde 7. A parallel series of reactions employing the isopropyl triene epimer 13a affords (±)-5-epi-sinularene. X-ray analyses of the triene 13a and the adduct 14a are also reported.

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