Angucyclinones Related to Ochromycinone. IV. The Structures and Reactions of Unusual Diels-Alder Adducts Formed from Maleic Anhydride and Racemic 5,5-Dimethyl-3-vinylcyclohex-2-en-1-ol

2000 ◽  
Vol 53 (5) ◽  
pp. 403 ◽  
Author(s):  
Craig Brinkworth ◽  
Tomas Rozek ◽  
John H. Bowie ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Carboxylic Acid ◽  
Maleic Anhydride ◽  
Anticancer Activity ◽  
Alder Reaction ◽  
Major Product ◽  
Diels Alder ◽  
Epoxide Ring ◽  
X Ray ◽  
Osmium Tetraoxide ◽  
Diels Alder Reaction

The Diels–Alder reaction between maleic anhydride and racemic 5,5-dimethyl-3-vinylcyclohex-2-en-1-ol gives two racemic diastereomers, the major product (2a,S,3R,8aS,8bR)-7,7-dimethyl-2-oxo-2a,3,4,6,7,8,8a,8b-octahydro-2H-benzo[cd]isobenzofuran-3-carboxylic acid (63% yield), and the minor product (2aR,3S,8aS,8bS)-7,7-dimethyl-2-oxo-2a,3,4,6,7,8,8a,8b-octahydro-2H-benzo[cd]isobenzofuran-3-carboxylic acid (9%). Epoxidation of the major product gives racemic (1aS,3R,3aS,5aR,8aS,8bR)-7,7-dimethyl-4 oxoperhydro-benzo[cd]oxireno[2,3-e]isobenzofuran-3-carboxylic acid in 81% yield, while opening of the epoxide ring gave the trans diol (2aS,3R,5S,5aR,8aR,8bR)-5,5a-dihydroxy-7,7-dimethyl-2-oxoperhydrobenzo[cd]isobenzofuran-3-carboxylic acid in 58% yield. Treatment of the major Diels–Alder product with osmium tetraoxide gave the cis diol (2aS,3R,5S,5aR,8aS,8bR)-5,5a-dihydroxy-7,7-dimethyl-2-oxoperhydrobenzo[cd]isobenzofuran-3-carboxylic acid in 86% yield. The structures of four products were confirmed by X-ray and n.m.r. methods. None of the products exhibit anticancer activity.

Structure reassignment of the major isomer from the Diels-Alder reaction of acryloyl chloride and 4,5,6,6a-tetrahydropentalene

1998 ◽  
Vol 76 (9) ◽  
pp. 1289-1293
Author(s):  
M Parvez ◽  
A Rauk ◽  
T S Sorensen ◽  
F Sun
Keyword(s):  
Carboxylic Acid ◽  
2D Nmr ◽  
Alder Reaction ◽  
Diels Alder ◽  
Acryloyl Chloride ◽  
X Ray ◽  
Diels Alder Reaction ◽  
Major Isomer ◽  
Facial Selectivity ◽  
Final Proof

After hydrogenation and hydrolysis, the two adducts formed from the Diels-Alder reaction of acryloyl chloride and 4,5,6,6a-tetrahydropentalene were originally assigned 7-exo- and 7-endo-carboxylic acid structures 3 and 4. Based on unexpected results in using these acids as starting materials for a superacid carbocation study, a reinvestigation of these structural assignments was carried out. From an extensive series of 2D NMR experiments, we conclude that 4 is correctly assigned, but that the other isomer is the 9-endo carboxylic acid 8. The formation of these two isomers (out of eight possible modes of addition) can be rationalized. Finally, an X-ray study of 8 was carried out as a final proof of structure.Key words: Diels-Alder reaction, facial selectivity, regioselectivity, X-ray structure, MO calculation.

Hetero-Diels-Alder Reactions of Enaminothione with Electrophilic Olefins. Synthesis of 2-Furyl Substituted 2H-Thiopyrans

2002 ◽  
Vol 57 (6) ◽  
pp. 637-644 ◽  
Author(s):  
Krystyna Bogdanowicz-Szwed ◽  
Artur Budzowski
Keyword(s):  
Acetic Acid ◽  
Maleic Anhydride ◽  
Acetic Anhydride ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diethyl Maleate ◽  
Diels Alder Reaction

AbstractThe hetero-Diels-Alder reaction of 1-(2-furyl)-3-(dimethylamino)-2-propene-1-thione (diene) with maleic and fumaric acids, and β-nitrostyrenes yielded 3,4-dihydro-2H-thiopyran derivatives. Treatment of some of those cycloadducts with acetic acid caused elimination of dimethylamine yielding stable 2H-thiopyrans. Reaction of the diene with maleic anhydride furnished a cycloadduct which underwent spontaneous rearrangement to form an N,N-dimethylamide derivative. Cycloadditions of the diene to maleimide, N-phenylmaleimide, diethyl maleate, fumarate and butenolide, carried out in the presence of acetic anhydride,were followed by elimination of dimethylamine, afforded stable 2H-thiopyran derivatives.

Reply to Comment on “Kinetics of a Diels−Alder Reaction of Maleic Anhydride and Isoprene in Supercritical CO2”

2003 ◽  
Vol 107 (43) ◽  
pp. 9249-9249 ◽  
Author(s):  
Evgeni M. Glebov ◽  
Larisa G. Krishtopa ◽  
Victor Stepanov ◽  
Lev N. Krasnoperov
Keyword(s):  
Maleic Anhydride ◽  
Supercritical Co2 ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction ◽  
Kinetics Of

scholarly journals Diastereoselective synthesis of novel spiro indanone fused pyrano[3,2-c]chromene derivatives following hetero-Diels–Alder reaction andin vitroanticancer studies

RSC Advances ◽  
2018 ◽  
Vol 8 (30) ◽  
pp. 16802-16814 ◽  
Author(s):  
Pravati Panda ◽  
Sabita Nayak ◽  
Susanta Ku. Sahoo ◽  
Seetaram Mohapatra ◽  
Deepika Nayak ◽  
...  
Keyword(s):  
Anticancer Activity ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diastereoselective Synthesis ◽  
Diels Alder Reaction

Synthesis of novel spiro indanone fused pyrano[3,2-c]chromene derivatives following hetero-Diels–Alder reaction has been demonstrated and evaluated for theirin vitroanticancer activity.

scholarly journals Crystal structure of (1S,2R,6R,7R,8S,12S)-4,10,17-triphenyl-15-thia-4,10-diazapentacyclo[5.5.5.01,16.02,6.08,12]heptadeca-13,16-diene-3,5,9,11-tetronep-xylene hemisolvate

2014 ◽  
Vol 70 (12) ◽  
pp. 550-554 ◽  
Author(s):  
Wayland E. Noland ◽  
Neil J. Kroll ◽  
Matthew P. Huisenga ◽  
Ruixian A. Yue ◽  
Simon B. Lang ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Alder Reaction ◽  
Major Product ◽  
Diels Alder ◽  
Inversion Center ◽  
Compound C ◽  
Diels Alder Reaction

The title tetrone compound, C32H22N2O4S· 0.5C8H10, is the major product (50% yield) of an attempted Diels–Alder reaction of 2-(α-styryl)thiophene withN-phenylmaleimide (2 equivalents) in toluene. Recrystallization of the resulting powder fromp-xylene gave the title hemisolvate; thep-xylene molecule is located about an inversion center. In the crystal, the primary tetrone contacts are between a carbonyl O atom and the four flagpole H atoms of the bicyclo[2.2.2]octene core, forming chains along [001].

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