e.g. Filippa Pettersson or Cancer Res. 75(6) , 1102-12, (2015) or 10.1002/anie.201600521

Stereoselective synthesis of an analog of podophyllotoxin by an intramolecular Diels-Alder reaction

…, PYS Lam, MM Mansuri, LM Speltz

Index: Jung, Michael E.; Lam, Patrick Yuk-Sun; Mansuri, Muzzamil M.; Speltz, Laurine M. Journal of Organic Chemistry, 1985 , vol. 50, # 7 p. 1087 - 1105

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Citation Number: 83

Abstract

The dihydrobenzocyclobutene 90 having a 4-hydroxycrotonate unit attached via an ester linkage as an internal dienophile can be cyclized to a 3: l mixture of the trans lactone 92 (an analogue of podophyllotoxin, 1) and the cis lactone 93. This stereoselective reaction proceeds via the intermediacy of the o-quinodimethane 91 which cyclizes from the endo transition state 91n in preference to the exo-one 91x, presumably because of stabilization ...

6-Bromopiperonal Structure

6-Bromopiperonal

Trimethyl orthoformate Structure

Trimethyl ortho...

~99%

5-bromo-6-(dimethoxymethyl)-1,3-benzodioxole Structure

5-bromo-6-(dime...

piperonal Structure

~%

5-bromo-6-(dimethoxymethyl)-1,3-benzodioxole Structure

5-bromo-6-(dime...

Benzyltriphenylphosphonium bromide Structure

Benzyltriphenyl...

~%

2-(1,3-Benzodioxol-5-yl)-1-phenylethanone Structure

2-(1,3-Benzodio...

6-Bromopiperonal Structure

6-Bromopiperonal

~%

2-(1,3-Benzodioxol-5-yl)-1-phenylethanone Structure

2-(1,3-Benzodio...

Benzyl bromide Structure

~%

2-(1,3-Benzodioxol-5-yl)-1-phenylethanone Structure

2-(1,3-Benzodio...

(E)-6-bromo-5-(2-phenyl-1,2-epoxyethyl)benzo-1,3-doxole Structure

(E)-6-bromo-5-(...

~5%

2-(1,3-Benzodioxol-5-yl)-1-phenylethanone Structure

2-(1,3-Benzodio...

Cyclobuta[f]-1,3-benzodioxol-5-ol, 5,6-dihydro-5-phenyl Structure

Cyclobuta[f]-1,...

(E)-6-bromo-5-(2-phenylethenyl)benzo-1,3-dioxole Structure

(E)-6-bromo-5-(...

~%

2-(1,3-Benzodioxol-5-yl)-1-phenylethanone Structure

2-(1,3-Benzodio...

methyl 4-hydroxybut-2-enoate Structure

methyl 4-hydrox...

N/A Structure

~0%

1,3-Dicyclohexylurea Structure

1,3-Dicyclohexylurea

N/A Structure

4-Bromo-2,6-dimethoxyphenol Structure

4-Bromo-2,6-dim...

Dimethyl sulfate Structure

Dimethyl sulfate

~79%

5-Bromo-1,2,3-trimethoxybenzene Structure

5-Bromo-1,2,3-t...

Syringol Structure

~%

5-Bromo-1,2,3-trimethoxybenzene Structure

5-Bromo-1,2,3-t...

6-bromobenzo-1,3-dioxole-5-propanonitrile Structure

6-bromobenzo-1,...

~81%

5-cyano-5,6-dihydrocyclobuta(f)-1,3-benzodioxole Structure

5-cyano-5,6-dih...

α-cyano-6-bromobenzo-1,3-dioxole-5-propanoic acid Structure

α-cyano-6-bromo...

~%

5-cyano-5,6-dihydrocyclobuta(f)-1,3-benzodioxole Structure

5-cyano-5,6-dih...

3,4-Methylenedioxyacetophenone Structure

3,4-Methylenedi...

Dimethyl Carbonate Structure

Dimethyl Carbonate

~%

Methyl 3-(1,3-benzodioxol-5-yl)-3-oxopropanoate Structure

Methyl 3-(1,3-b...

6-Bromopiperonal Structure

6-Bromopiperonal

~93%

5-BROMO-6-NITROBENZO[D][1,3]DIOXOLE Structure

5-BROMO-6-NITRO...

5-BROMO-6-NITROBENZO[D][1,3]DIOXOLE Structure

5-BROMO-6-NITRO...

~%

5-BROMO-6-IODOBENZO[D][1,3]DIOXOLE Structure

5-BROMO-6-IODOB...

piperonal Structure

~%

5-BROMO-6-IODOBENZO[D][1,3]DIOXOLE Structure

5-BROMO-6-IODOB...

6-Bromopiperonal Structure

6-Bromopiperonal

~%

5-BROMO-6-IODOBENZO[D][1,3]DIOXOLE Structure

5-BROMO-6-IODOB...

5-amino-6-bromobenzo-1,3-dioxole hydrochloride Structure

5-amino-6-bromo...

~%

5-BROMO-6-IODOBENZO[D][1,3]DIOXOLE Structure

5-BROMO-6-IODOB...

piperonal Structure

~%

Cyclobuta[f]-1,3-benzodioxol-5-ol, 5,6-dihydro-5-phenyl Structure

Cyclobuta[f]-1,...

Benzyltriphenylphosphonium bromide Structure

Benzyltriphenyl...

~%

Cyclobuta[f]-1,3-benzodioxol-5-ol, 5,6-dihydro-5-phenyl Structure

Cyclobuta[f]-1,...

6-Bromopiperonal Structure

6-Bromopiperonal

~%

Cyclobuta[f]-1,3-benzodioxol-5-ol, 5,6-dihydro-5-phenyl Structure

Cyclobuta[f]-1,...

Benzyl bromide Structure

~%

Cyclobuta[f]-1,3-benzodioxol-5-ol, 5,6-dihydro-5-phenyl Structure

Cyclobuta[f]-1,...

(E)-6-bromo-5-(2-phenyl-1,2-epoxyethyl)benzo-1,3-doxole Structure

(E)-6-bromo-5-(...

~33%

2-(1,3-Benzodioxol-5-yl)-1-phenylethanone Structure

2-(1,3-Benzodio...

Cyclobuta[f]-1,3-benzodioxol-5-ol, 5,6-dihydro-5-phenyl Structure

Cyclobuta[f]-1,...

(E)-6-bromo-5-(2-phenylethenyl)benzo-1,3-dioxole Structure

(E)-6-bromo-5-(...

~%

Cyclobuta[f]-1,3-benzodioxol-5-ol, 5,6-dihydro-5-phenyl Structure

Cyclobuta[f]-1,...

piperonal Structure

~%

5-Bromo-6-fluorobenzo[d][1,3]dioxole Structure

5-Bromo-6-fluor...

2-bromo-4,5-methylenedioxyaniline Structure

2-bromo-4,5-met...

~%

5-Bromo-6-fluorobenzo[d][1,3]dioxole Structure

5-Bromo-6-fluor...

5-BROMO-6-NITROBENZO[D][1,3]DIOXOLE Structure

5-BROMO-6-NITRO...

~%

5-Bromo-6-fluorobenzo[d][1,3]dioxole Structure

5-Bromo-6-fluor...

6-Bromopiperonal Structure

6-Bromopiperonal

~%

5-Bromo-6-fluorobenzo[d][1,3]dioxole Structure

5-Bromo-6-fluor...

6-bromobenzo-1,3-dioxole-5-diazonium tetrafluoroborate Structure

6-bromobenzo-1,...

~12%

5-Bromo-6-fluorobenzo[d][1,3]dioxole Structure

5-Bromo-6-fluor...

5-amino-6-bromobenzo-1,3-dioxole hydrochloride Structure

5-amino-6-bromo...

~%

5-Bromo-6-fluorobenzo[d][1,3]dioxole Structure

5-Bromo-6-fluor...

Furan Structure

5-BROMO-6-IODOBENZO[D][1,3]DIOXOLE Structure

5-BROMO-6-IODOB...

~90%

5,8-Epoxynaphtho[2,3-d]-1,3-dioxole, 5,8-dihydro Structure

5,8-Epoxynaphth...

piperonal Structure

~%

5,8-Epoxynaphtho[2,3-d]-1,3-dioxole, 5,8-dihydro Structure

5,8-Epoxynaphth...

2-bromo-4,5-methylenedioxyaniline Structure

2-bromo-4,5-met...

~%

5,8-Epoxynaphtho[2,3-d]-1,3-dioxole, 5,8-dihydro Structure

5,8-Epoxynaphth...

5-BROMO-6-NITROBENZO[D][1,3]DIOXOLE Structure

5-BROMO-6-NITRO...

~%

5,8-Epoxynaphtho[2,3-d]-1,3-dioxole, 5,8-dihydro Structure

5,8-Epoxynaphth...

6-Bromopiperonal Structure

6-Bromopiperonal

~%

5,8-Epoxynaphtho[2,3-d]-1,3-dioxole, 5,8-dihydro Structure

5,8-Epoxynaphth...

5-amino-6-bromobenzo-1,3-dioxole hydrochloride Structure

5-amino-6-bromo...

~%

5,8-Epoxynaphtho[2,3-d]-1,3-dioxole, 5,8-dihydro Structure

5,8-Epoxynaphth...

Comprehensive synthetic route to eight diastereomeric Podoph...

[Forsey, Steven P.; Rajapaksa, Dayananda; Taylor, Nicholas J.; Rodrigo, Russell Journal of Organic Chemistry, 1989 , vol. 54, # 18 p. 4280 - 4290]