Stereocontrolled construction of A.B.C.[6.6.6] tricycle via transannular Diels–Alder reaction of 14-membered macrocycle with acetylene as dienophile

1990 ◽  
Vol 68 (12) ◽  
pp. 2137-2143 ◽  
Author(s):  
Yao-Chang Xu ◽  
Michel Cantin ◽  
Pierre Deslongchamps
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
The Other ◽  
One Pot ◽  
Diels Alder Reaction ◽  
Other Hand ◽  
Tricyclic Compound ◽  
Stereocontrolled Synthesis ◽  
Allylic Chloride

The syntheses of the acyclic dienynes 14a (cis-trans-acetylene) and 14b (trans-trans-acetylene) are described. The tandem macrocyclization and transannular Diels–Alder reaction of the allylic chloride 14b was conducted in the presence of Cs2CO3 at 85 °C in one-pot to provide tricyclic product 16, with the two hydrogens in ring B being cis. On the other hand, treatment of the allylic chloride 14a under the same conditions afforded 14-membered macrocycle 17, which could be transformed at 250 °C into a similar tricyclic product 18 with the two hydrogens in ring B being trans, along with an interesting by-product 19. The mechanism for the formation of 19 is also discussed. Keywords: stereocontrolled synthesis, macrocycle, tricyclic compound, transannular Diels–Alder reaction.

Synthesis and transannular Diels–Alder reaction of a 13-membered macrocyclic triene having a tetrasubstituted enol ether as dienophile

1990 ◽  
Vol 68 (3) ◽  
pp. 404-411 ◽  
Author(s):  
Gervais Bérubé ◽  
Pierre Deslongchamps
Keyword(s):  
Organic Synthesis ◽  
Alder Reaction ◽  
Diels Alder ◽  
The Other ◽  
Enol Ether ◽  
Diels Alder Reaction ◽  
Other Hand ◽  
Tricyclic Compounds

The syntheses of the acyclic triene trans–trans–cis27 and trans–trans–trans31 are described. Macrocyclization and concomitant transannular Diels–Alder reaction were performed with the chloride derivative obtained from the trans–trans–cis triene alcohol 27 yielding a mixture of the tricyclic compounds trans–syn–trans33 and cis–syn–cis34. On the other hand, macrocyclization of the chloride derived from trans–trans–trans triene 31 was not successful. Keywords: transannular process, Diels–Alder reaction, macrocyclic triene, macrocyclization, tricyclic compounds, organic synthesis.

Preparation and Properties of Rubberlike High Polymers. II. Polymerization of Mixtures in Bulk

1947 ◽  
Vol 20 (2) ◽  
pp. 380-391
Author(s):  
C. Koningsberger ◽  
G. Salomon
Keyword(s):  
Mechanical Properties ◽  
Alder Reaction ◽  
Diels Alder ◽  
The Other ◽  
New Class ◽  
Diels Alder Reaction ◽  
Vinyl Compound ◽  
Other Hand ◽  
Higher Temperature ◽  
High Polymers

Abstract Mixtures of butadiene and dimethylbutadiene with varying quantities of styrene and acrylonitrile were copolymerized under various catalytic conditions at 100° C. The formation of cyclic dimers from dienes and vinyl compounds is, in some cases, much more pronounced than the dimerization of the dienes alone. Since the latter is also a kind of Diels-Alder reaction, a series with increasing dienophilic properties can be established from a comparison of the yields of cyclic dimers. From solubility and swelling experiments it is evident that the polymers prepared from butadiene and the vinyl compounds and those from dimethylbutadiene and acrylonitrile are true copolymers. The mechanical properties of the copolymers from butadiene and increasing amounts of a vinyl compound change gradually from those of a rubber to those of the polyvinyl compound. The copolymers from a mixture containing 30 per cent styrene or acrylonitrile are very similar to Buna-S and Perbunan, respectively. Copolymers of the same composition from dimethylbutadiene and acrylonitrile, on the other hand, form a new class of thermoplastics with a much higher temperature of elasticity.

Stereocontrolled construction of A.B.C.[6.6.6] tricycle via transannular Diels–Alder reaction of 14-membered triene macrocycle

1990 ◽  
Vol 68 (12) ◽  
pp. 2144-2152 ◽  
Author(s):  
Michel Cantin ◽  
Yao-Chang Xu ◽  
Pierre Deslongchamps
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
Excellent Yield ◽  
Diels Alder Reaction ◽  
Tricyclic Compound ◽  
Stereocontrolled Synthesis

The synthesis of the four acyclic trienes 11a, b and 20a, b is reported. The tandem macrocyclization and stereoselective transannular Diels–Alder reaction of acyclic trienes 11b (trans-trans-cis) and 20b (trans-trans-trans) were observed in the presence of Cs2CO3 at 85 °C to give tricycles 30 (TST) and 32 (CAT) respectively. However, treatment of acyclic trienes 11a (cis-trans-cis) and 20a (cis-trans-trans) under the same conditions yielded the 14-membered macrocycles 21 and 23, which were stereoselectively transformed at 250 °C into tricycles 22 (CST) and 24 (CAT) respectively in excellent yield. Keywords: stereocontrolled synthesis, macrocycle, tricyclic compound, transannular Diels–Alder reaction.

Aza-Diels-Alder Reaction Between 1,2-Diaza-1,3-dienes and β-Aryl-α,β-unsaturated Carbonyl Compounds. Easy One-pot Entry to 2’-Oxo-imidazo[1’,5’- f]tetrahydropyridazine

2014 ◽  
Vol 10 (6) ◽  
pp. 951-960
Author(s):  
Orazio Attanasi ◽  
Luca Bianchi ◽  
Maurizio D’Auria ◽  
Gianfranco Favi ◽  
Fabio Mantellini ◽  
...  
Keyword(s):  
Carbonyl Compounds ◽  
Alder Reaction ◽  
Diels Alder ◽  
One Pot ◽  
Diels Alder Reaction

scholarly journals One-Pot and Metal-Free Synthesis of 3-Arylated 4-Nitrophenols via Polyfunctionalized Cyclohexanones from β-Nitrostyrenes

2020 ◽  
Author(s):  
Haruyasu Asahara ◽  
Minami Hiraishi ◽  
Nagatoshi Nishiwaki
Keyword(s):  
Dimethyl Sulfoxide ◽  
Catalytic Amount ◽  
Alder Reaction ◽  
Diels Alder ◽  
One Pot ◽  
Metal Free ◽  
Diels Alder Reaction ◽  
Thienyl Group ◽  
Danishefsky's Diene

β-Nitrostyrenes underwent the Diels-Alder reaction with Danishefsky’s diene to afford cyclohexenes together with the corresponding hydrolyzed products, 3-arylated 5-methoxy-4-nitrocyclohexanones. When the reaction was conducted in the presence of water, the cyclohexenes were efficiently hydrolyzed into cyclohexanones. Subsequent aromatization by heating the cyclohexanone with a catalytic amount of iodine in dimethyl sulfoxide gave 3-arylated 4-nitrophenols. The reaction of nitrostyrenes with Danishefsky’s diene could be conducted in one-pot to directly afford the corresponding nitrophenols. Moreover, a heteroaryl group such as a thienyl group could be introduced into the nitrophenol framework.

scholarly journals Bicyclic allyltin derivatives through selective “one pot” hydrostannation - Diels-Alder reaction

ARKIVOC ◽  
2011 ◽  
Vol 2011 (7) ◽  
pp. 195-209 ◽  
Author(s):  
Romina A. Ocampo ◽  
Sandra D. Mandolesi ◽  
Liliana C. Koll
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
One Pot ◽  
Diels Alder Reaction
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