Synthesis of a Substituted Bi[cyclohepta-3,5(3′,5′)-dienyl]: A Possible Building Block for Domino Diels−Alder Reactions

Abstract

A versatile 13‐step synthesis of 1,1′‐dimethoxy‐4,4′,5,5′‐tetrakis(trimethylsilyloxy)bicyclohepta‐3,3′,5,5′‐dienyl (11) is described. 11 represents a potential building block for the construction of polycyclic cage compounds through domino Diels−Alder and pincer reactions.

Attempted [2]Catenane Synthesis via a Quasi[1]catenane by a Templated Backfolding Strategy

“…To activate the ketone moiety, it was first reacted with excess trimethyl orthoformate in methanol, forming acetal 8 (see Scheme 3). [3] Note that under these conditions the ethyl esters were transformed to methyl esters. Subsequent acid catalyzed trans-acetalization with dimethyl tartrate was conducted next.…”

“…Although orthogonally protected esters would be most desirable, it was decided to first test the ketal formation with dimethyl tartrate 9 and diethyl 4‐oxopimelate 7 (both commercially available). To activate the ketone moiety, it was first reacted with excess trimethyl orthoformate in methanol, forming acetal 8 (see Scheme ) . Note that under these conditions the ethyl esters were transformed to methyl esters.…”

Attempted [2]Catenane Synthesis via a Quasi[1]catenane by a Templated Backfolding Strategy

“…To activate the ketone moiety, it was first reacted with excess trimethyl orthoformate in methanol, forming acetal 8 (see Scheme 3). [3] Note that under these conditions the ethyl esters were transformed to methyl esters. Subsequent acid catalyzed trans-acetalization with dimethyl tartrate was conducted next.…”

“…Although orthogonally protected esters would be most desirable, it was decided to first test the ketal formation with dimethyl tartrate 9 and diethyl 4‐oxopimelate 7 (both commercially available). To activate the ketone moiety, it was first reacted with excess trimethyl orthoformate in methanol, forming acetal 8 (see Scheme ) . Note that under these conditions the ethyl esters were transformed to methyl esters.…”

Synthesis of Diketones, Ketoesters, and Tetraketones by Electrochemical Oxidative Decarboxylation of Malonic Acid Derivatives: Application to the Synthesis of cis-Jasmone

“…Colorless liquid, 75 mg, 74% yield. Spectroscopic data matched those previously reported in the literature …”

Recent advances of carbonyl olefination via McMurry coupling reaction

“… 13 Moreover, Sander and Dehmlow successfully synthesized 1-( cis -4′,5′-dihydroxycycloheptylidene)- cis -4,5-dihydroxycycloheptane, 6, through McMurry coupling of the cis -4,5-dibenzyloxycycloheptanone compound, 5. 35 …”

“…13 Moreover, Sander and Dehmlow successfully synthesized 1-(cis-4 0 ,5 0 -dihydroxycycloheptylidene)-cis-4,5-dihydroxycycloheptane, 6, through McMurry coupling of the cis-4,5-dibenzyloxycycloheptanone compound, 5. 35 4.1.2 Alcohol (saturated alcohol complex and some aromatic alcohol). Some experiments have tested the compatibility of the alcohol groups in the McMurry reaction (Fig.…”

Attempted [2]Catenane Synthesis via a Quasi[1]catenane by a Templated Backfolding Strategy

“…To activate the ketone moiety, it was first reacted with excess trimethyl orthoformate in methanol, forming acetal 8 (see Scheme 3). [3] Note that under these conditions the ethyl esters were transformed to methyl esters. Subsequent acid catalyzed trans-acetalization with dimethyl tartrate was conducted next.…”

“…Although orthogonally protected esters would be most desirable, it was decided to first test the ketal formation with dimethyl tartrate 9 and diethyl 4‐oxopimelate 7 (both commercially available). To activate the ketone moiety, it was first reacted with excess trimethyl orthoformate in methanol, forming acetal 8 (see Scheme ) . Note that under these conditions the ethyl esters were transformed to methyl esters.…”

Synthesis of Diketones, Ketoesters, and Tetraketones by Electrochemical Oxidative Decarboxylation of Malonic Acid Derivatives: Application to the Synthesis of cis-Jasmone

“…Colorless liquid, 75 mg, 74% yield. Spectroscopic data matched those previously reported in the literature …”

Recent advances of carbonyl olefination via McMurry coupling reaction

“… 13 Moreover, Sander and Dehmlow successfully synthesized 1-( cis -4′,5′-dihydroxycycloheptylidene)- cis -4,5-dihydroxycycloheptane, 6, through McMurry coupling of the cis -4,5-dibenzyloxycycloheptanone compound, 5. 35 …”

“…13 Moreover, Sander and Dehmlow successfully synthesized 1-(cis-4 0 ,5 0 -dihydroxycycloheptylidene)-cis-4,5-dihydroxycycloheptane, 6, through McMurry coupling of the cis-4,5-dibenzyloxycycloheptanone compound, 5. 35 4.1.2 Alcohol (saturated alcohol complex and some aromatic alcohol). Some experiments have tested the compatibility of the alcohol groups in the McMurry reaction (Fig.…”

Attempted [2]Catenane Synthesis via a Quasi[1]catenane by a Templated Backfolding Strategy

“…To activate the ketone moiety, it was first reacted with excess trimethyl orthoformate in methanol, forming acetal 8 (see Scheme 3). [3] Note that under these conditions the ethyl esters were transformed to methyl esters. Subsequent acid catalyzed trans-acetalization with dimethyl tartrate was conducted next.…”

“…Although orthogonally protected esters would be most desirable, it was decided to first test the ketal formation with dimethyl tartrate 9 and diethyl 4‐oxopimelate 7 (both commercially available). To activate the ketone moiety, it was first reacted with excess trimethyl orthoformate in methanol, forming acetal 8 (see Scheme ) . Note that under these conditions the ethyl esters were transformed to methyl esters.…”

Synthesis of Diketones, Ketoesters, and Tetraketones by Electrochemical Oxidative Decarboxylation of Malonic Acid Derivatives: Application to the Synthesis of cis-Jasmone

“…Colorless liquid, 75 mg, 74% yield. Spectroscopic data matched those previously reported in the literature …”

Recent advances of carbonyl olefination via McMurry coupling reaction

“… 13 Moreover, Sander and Dehmlow successfully synthesized 1-( cis -4′,5′-dihydroxycycloheptylidene)- cis -4,5-dihydroxycycloheptane, 6, through McMurry coupling of the cis -4,5-dibenzyloxycycloheptanone compound, 5. 35 …”

“…13 Moreover, Sander and Dehmlow successfully synthesized 1-(cis-4 0 ,5 0 -dihydroxycycloheptylidene)-cis-4,5-dihydroxycycloheptane, 6, through McMurry coupling of the cis-4,5-dibenzyloxycycloheptanone compound, 5. 35 4.1.2 Alcohol (saturated alcohol complex and some aromatic alcohol). Some experiments have tested the compatibility of the alcohol groups in the McMurry reaction (Fig.…”