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.

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.

Stereo-controlled synthesis of polyheterocycles via the diene-transmissive hetero-Diels–Alder reaction of β,γ-unsaturated α-keto esters

2015 ◽  
Vol 13 (21) ◽  
pp. 5875-5879 ◽  
Author(s):  
Takashi Otani ◽  
Yumiko Tamai ◽  
Kazunori Seki ◽  
Tomohiro Kikuchi ◽  
Taiichiro Miyazawa ◽  
...  
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
Controlled Synthesis ◽  
Keto Esters ◽  
Diels Alder Reaction ◽  
Stereocontrolled Synthesis

Stereocontrolled synthesis of polyheterocycles via the diene-transmissive hetero Diels–Alder reaction of β,χ-unsaturated α-keto esters is described.

First hetero-diels-alder reaction of an enantiopure 2-sulfinylbuta-1, 3-diene: mild and effective stereocontrolled synthesis of pyranoid derivatives

1997 ◽  
Vol 8 (17) ◽  
pp. 2989-2995 ◽  
Author(s):  
Maria C. Aversa ◽  
Anna Barattucci ◽  
Paola Bonaccorsi ◽  
Giuseppe Bruno ◽  
Placido Giannetto ◽  
...  
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction ◽  
Stereocontrolled Synthesis

Stereocontrolled construction of 1,7-dimethyl A.B.C.[6.6.6] tricycles. Part I. Transannular Diels–Alder reactions of 14-membered macrocycles containing trans-dienophiles

1993 ◽  
Vol 71 (8) ◽  
pp. 1152-1168 ◽  
Author(s):  
Yao-Chang Xu ◽  
Andrew L. Roughton ◽  
Raymond Plante ◽  
Solo Goldstein ◽  
Pierre Deslongchamps
Keyword(s):  
Natural Products ◽  
Alder Reaction ◽  
Diels Alder ◽  
Methyl Substituent ◽  
Dimethyl Malonate ◽  
General Methodology ◽  
Racemic Form ◽  
Diels Alder Reaction ◽  
Tricyclic Compounds ◽  
Stereocontrolled Synthesis

Transannular Diels–Alder reactions of 14-membered macrocyclic trienes possessing a methyl substituent on both the diene and dienophile moiety have been investigated. Macrocyclic structures 1a, 1b, and 1c having cis-trans-trans (CTT), trans-cis-trans (TCT), and trans-trans-trans (TTT) geometries could be stereoselectively constructed by coupling appropriately functionalized dienes 5 and dienophile 4 following an intramolecular displacement of an allylic halide by the anion of an appropriately located dimethyl malonate unit. The transannular Diels–Alder reaction performed on 1a led to a mixture of four major tricyclic products, including 34 possessing the unexpected trans-anti-cis (TAC) stereochemistry. When heated at 300 °C, macrocycle 1b underwent an unique conversion via an ene–retroene, Diels–Alder process, producing the unexpected tricycle 41 (racemic form) containing five contiguous chiral centers. A rationale for the above experimental facts is presented. In contrast to the previous results, the transannular Diels–Alder reaction of macrocycle 1c was straightforward, producing a 95% isolated yield of trans-anti-cis (TAC) tricycle 34. This investigation demonstrates a general methodology for the stereocontrolled synthesis of 1,2-dimethyl A.B.C[6.6.6] tricyclic compounds, which are potential precursors to polycyclic natural products such as steroids and terpenes.

scholarly journals Stereocontrolled chiral synthesis of a trans-anti-trans tricycle by a transannular Diels–Alder reaction

1992 ◽  
Vol 70 (9) ◽  
pp. 2350-2364 ◽  
Author(s):  
Anne Marinier ◽  
Pierre Deslongchamps
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
Chiral Synthesis ◽  
Diels Alder Reaction ◽  
Tricyclic Compound ◽  
Preliminary Study

The racemic and chiral synthesis of trans-cis-cis macrocyclic triene 5 is described. Heating this compound at 262 °C leads via a transannular Diels–Alder reaction to the tricyclic structure 6, which can be further transformed into tricyclic compound 7. This work constitutes a preliminary study for the synthesis of corticoids.

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