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

Stereocontrolled total synthesis of (.+-.)-pentenomycins. I-III, their epimers, and dehydropentenomycin I

…, SJ Branca, NN Pilla, MA Guaciaro

Index: Smith III; Branca; Pilla; Guaciaro Journal of Organic Chemistry, 1982 , vol. 47, # 10 p. 1855 - 1869

Full Text: HTML

Citation Number: 108

Abstract

The total synthesis of (f)-pentenomycins 1-111 (la-c), their epimers (2a-c) termed by us epipentenomycins (I-111), and dehydropentenomycin I (3), seven members of the novel cyclopentanoid class of antibiotics, has been achieved. The synthetic routes are short (ca. five to seven steps), stereocontrolled, and for the most part highly efficient. Key elements of the strategies were (i) the development of a versatile a-ketovinyl anion equivalent which ...

2-CYCLOPENTEN-1-ONE, 2-BROMO- Structure

2-CYCLOPENTEN-1...

Ethylene glycol Structure

Ethylene glycol

~82%

1,4-DIOXASPIRO[4.4]NON-6-ENE, 6-BROMO- Structure

1,4-DIOXASPIRO[...

2-Cyclopenten-1-one, 2-(hydroxymethyl)- Structure

2-Cyclopenten-1...

Ethanoic anhydride Structure

Ethanoic anhydride

~90%

Cyclopent-2-en-1-one, 2-acetyloxymethyl Structure

Cyclopent-2-en-...

6-carbethoxy-1,4-dioxaspiro[4.4]non-6-ene Structure

6-carbethoxy-1,...

~%

Cyclopent-2-en-1-one, 2-acetyloxymethyl Structure

Cyclopent-2-en-...

1,4-DIOXASPIRO[4.4]NON-6-ENE, 6-BROMO- Structure

1,4-DIOXASPIRO[...

~%

Cyclopent-2-en-1-one, 2-acetyloxymethyl Structure

Cyclopent-2-en-...

2-CYCLOPENTEN-1-ONE, 2-BROMO- Structure

2-CYCLOPENTEN-1...

~%

Cyclopent-2-en-1-one, 2-acetyloxymethyl Structure

Cyclopent-2-en-...

ethyl 5-oxocyclopentene-1-carboxylate Structure

ethyl 5-oxocycl...

~%

Cyclopent-2-en-1-one, 2-acetyloxymethyl Structure

Cyclopent-2-en-...

6-carbethoxy-1,4-dioxaspiro[4.4]non-6-ene Structure

6-carbethoxy-1,...

~%

2-[[tert-butyl(dimethyl)silyl]oxymethyl]cyclopent-2-en-1-one Structure

2-[[tert-butyl(...

1,4-DIOXASPIRO[4.4]NON-6-ENE, 6-BROMO- Structure

1,4-DIOXASPIRO[...

~%

2-[[tert-butyl(dimethyl)silyl]oxymethyl]cyclopent-2-en-1-one Structure

2-[[tert-butyl(...

2-CYCLOPENTEN-1-ONE, 2-BROMO- Structure

2-CYCLOPENTEN-1...

~%

2-[[tert-butyl(dimethyl)silyl]oxymethyl]cyclopent-2-en-1-one Structure

2-[[tert-butyl(...

ethyl 5-oxocyclopentene-1-carboxylate Structure

ethyl 5-oxocycl...

~%

2-[[tert-butyl(dimethyl)silyl]oxymethyl]cyclopent-2-en-1-one Structure

2-[[tert-butyl(...

cis-4,5-dihydroxy-5-[[(tert-butyldimethylsilyl)oxy]methyl]-2-cyclopentenone Structure

cis-4,5-dihydro...

~93%

2-Cyclopenten-1-one,4,5-dihydroxy-5-(hydroxymethyl)-, (4R,5R)-rel- Structure

2-Cyclopenten-1...

t-4-[(tert-butyldimethylsilyl)oxy]-5-hydroxy-r-5-[[(tert-butyldimethylsilyl)oxy]methyl]-2-cyclopentenone Structure

t-4-[(tert-buty...

~96%

2-Cyclopenten-1-one,4,5-dihydroxy-5-(hydroxymethyl)-, (4R,5R)-rel- Structure

2-Cyclopenten-1...

6-carbethoxy-1,4-dioxaspiro[4.4]non-6-ene Structure

6-carbethoxy-1,...

~%

2-Cyclopenten-1-one,4,5-dihydroxy-5-(hydroxymethyl)-, (4R,5R)-rel- Structure

2-Cyclopenten-1...

1,4-DIOXASPIRO[4.4]NON-6-ENE, 6-BROMO- Structure

1,4-DIOXASPIRO[...

~%

2-Cyclopenten-1-one,4,5-dihydroxy-5-(hydroxymethyl)-, (4R,5R)-rel- Structure

2-Cyclopenten-1...

2-CYCLOPENTEN-1-ONE, 2-BROMO- Structure

2-CYCLOPENTEN-1...

~%

2-Cyclopenten-1-one,4,5-dihydroxy-5-(hydroxymethyl)-, (4R,5R)-rel- Structure

2-Cyclopenten-1...

2-Cyclopenten-1-one, 2-(hydroxymethyl)- Structure

2-Cyclopenten-1...

~%

2-Cyclopenten-1-one,4,5-dihydroxy-5-(hydroxymethyl)-, (4R,5R)-rel- Structure

2-Cyclopenten-1...

2-[[tert-butyl(dimethyl)silyl]oxymethyl]cyclopent-2-en-1-one Structure

2-[[tert-butyl(...

~%

2-Cyclopenten-1-one,4,5-dihydroxy-5-(hydroxymethyl)-, (4R,5R)-rel- Structure

2-Cyclopenten-1...

ethyl 5-oxocyclopentene-1-carboxylate Structure

ethyl 5-oxocycl...

~%

2-Cyclopenten-1-one,4,5-dihydroxy-5-(hydroxymethyl)-, (4R,5R)-rel- Structure

2-Cyclopenten-1...

cis-2,3-dihydroxy-2-[[(tert-butyldimethylsilyl)oxy]methyl]cyclopentanone Structure

cis-2,3-dihydro...

~%

2-Cyclopenten-1-one,4,5-dihydroxy-5-(hydroxymethyl)-, (4R,5R)-rel- Structure

2-Cyclopenten-1...

t-3-[(tert-butyldimethylsilyl)oxy]-2-hydroxy-r-2-[[(tert-butyldimethylsilyl)oxy]methyl]cyclopentanone Structure

t-3-[(tert-buty...

~%

2-Cyclopenten-1-one,4,5-dihydroxy-5-(hydroxymethyl)-, (4R,5R)-rel- Structure

2-Cyclopenten-1...

6-carbethoxy-1,4-dioxaspiro[4.4]non-6-ene Structure

6-carbethoxy-1,...

~%

2-Cyclopenten-1-one, 2-(hydroxymethyl)- Structure

2-Cyclopenten-1...

1,4-DIOXASPIRO[4.4]NON-6-ENE, 6-BROMO- Structure

1,4-DIOXASPIRO[...

~%

2-Cyclopenten-1-one, 2-(hydroxymethyl)- Structure

2-Cyclopenten-1...

2-CYCLOPENTEN-1-ONE, 2-BROMO- Structure

2-CYCLOPENTEN-1...

~%

2-Cyclopenten-1-one, 2-(hydroxymethyl)- Structure

2-Cyclopenten-1...

ethyl 5-oxocyclopentene-1-carboxylate Structure

ethyl 5-oxocycl...

~%

2-Cyclopenten-1-one, 2-(hydroxymethyl)- Structure

2-Cyclopenten-1...

2-Bromo-3-methylcyclopent-2-en-1-one Structure

2-Bromo-3-methy...

Ethylene glycol Structure

Ethylene glycol

~90%

9-bromo-8-methyl-1,4-dioxaspiro[4.4]non-8-ene Structure

9-bromo-8-methy...

3-Methyl-2-cyclopenten-1-one Structure

3-Methyl-2-cycl...

~%

9-bromo-8-methyl-1,4-dioxaspiro[4.4]non-8-ene Structure

9-bromo-8-methy...

cyclohexenone Structure

~%

6-bromo-1,4-dioxaspiro[4.5]dec-6-ene Structure

6-bromo-1,4-dio...

2-CYCLOPENTEN-1-ONE, 2-BROMO- Structure

2-CYCLOPENTEN-1...

~%

2-methylsulfanylcyclopent-2-en-1-one Structure

2-methylsulfany...

1,4-DIOXASPIRO[4.4]NON-6-ENE, 6-BROMO- Structure

1,4-DIOXASPIRO[...

Dimethyl disulfide Structure

Dimethyl disulfide

~%

2-methylsulfanylcyclopent-2-en-1-one Structure

2-methylsulfany...

t-4-acetoxy-5-hydroxy-r-5-[[(tert-butyldimethylsilyl)oxy]methyl]-2-cyclopentenone Structure

t-4-acetoxy-5-h...

~88%

[5-hydroxy-5-(hydroxymethyl)-4-oxo-1-cyclopent-2-enyl] acetate Structure

[5-hydroxy-5-(h...

6-carbethoxy-1,4-dioxaspiro[4.4]non-6-ene Structure

6-carbethoxy-1,...

~%

[5-hydroxy-5-(hydroxymethyl)-4-oxo-1-cyclopent-2-enyl] acetate Structure

[5-hydroxy-5-(h...

1,4-DIOXASPIRO[4.4]NON-6-ENE, 6-BROMO- Structure

1,4-DIOXASPIRO[...

~%

[5-hydroxy-5-(hydroxymethyl)-4-oxo-1-cyclopent-2-enyl] acetate Structure

[5-hydroxy-5-(h...

2-CYCLOPENTEN-1-ONE, 2-BROMO- Structure

2-CYCLOPENTEN-1...

~%

[5-hydroxy-5-(hydroxymethyl)-4-oxo-1-cyclopent-2-enyl] acetate Structure

[5-hydroxy-5-(h...

2-Cyclopenten-1-one, 2-(hydroxymethyl)- Structure

2-Cyclopenten-1...

~%

[5-hydroxy-5-(hydroxymethyl)-4-oxo-1-cyclopent-2-enyl] acetate Structure

[5-hydroxy-5-(h...

2-[[tert-butyl(dimethyl)silyl]oxymethyl]cyclopent-2-en-1-one Structure

2-[[tert-butyl(...

~%

[5-hydroxy-5-(hydroxymethyl)-4-oxo-1-cyclopent-2-enyl] acetate Structure

[5-hydroxy-5-(h...

ethyl 5-oxocyclopentene-1-carboxylate Structure

ethyl 5-oxocycl...

~%

[5-hydroxy-5-(hydroxymethyl)-4-oxo-1-cyclopent-2-enyl] acetate Structure

[5-hydroxy-5-(h...

cis-2,3-dihydroxy-2-[[(tert-butyldimethylsilyl)oxy]methyl]cyclopentanone Structure

cis-2,3-dihydro...

~%

[5-hydroxy-5-(hydroxymethyl)-4-oxo-1-cyclopent-2-enyl] acetate Structure

[5-hydroxy-5-(h...

cis-4,5-dihydroxy-5-[[(tert-butyldimethylsilyl)oxy]methyl]-2-cyclopentenone Structure

cis-4,5-dihydro...

~%

[5-hydroxy-5-(hydroxymethyl)-4-oxo-1-cyclopent-2-enyl] acetate Structure

[5-hydroxy-5-(h...

t-3-acetoxy-2-hydroxy-r-2-[[(tert-butyldimethylsilyl)oxy]methyl]cyclopentanone Structure

t-3-acetoxy-2-h...

~%

[5-hydroxy-5-(hydroxymethyl)-4-oxo-1-cyclopent-2-enyl] acetate Structure

[5-hydroxy-5-(h...

2-hydroxy-2-[[(tert-butyldimethylsilyl)oxy]methyl]cyclopent-4-ene-1,3-dione Structure

2-hydroxy-2-[[(...

~75%

2-hydroxy-2-(hydroxymethyl)cyclopent-4-ene-1,3-dione Structure

2-hydroxy-2-(hy...

6-carbethoxy-1,4-dioxaspiro[4.4]non-6-ene Structure

6-carbethoxy-1,...

~%

2-hydroxy-2-(hydroxymethyl)cyclopent-4-ene-1,3-dione Structure

2-hydroxy-2-(hy...

1,4-DIOXASPIRO[4.4]NON-6-ENE, 6-BROMO- Structure

1,4-DIOXASPIRO[...

~%

2-hydroxy-2-(hydroxymethyl)cyclopent-4-ene-1,3-dione Structure

2-hydroxy-2-(hy...

2-CYCLOPENTEN-1-ONE, 2-BROMO- Structure

2-CYCLOPENTEN-1...

~%

2-hydroxy-2-(hydroxymethyl)cyclopent-4-ene-1,3-dione Structure

2-hydroxy-2-(hy...

2-Cyclopenten-1-one, 2-(hydroxymethyl)- Structure

2-Cyclopenten-1...

~%

2-hydroxy-2-(hydroxymethyl)cyclopent-4-ene-1,3-dione Structure

2-hydroxy-2-(hy...

2-[[tert-butyl(dimethyl)silyl]oxymethyl]cyclopent-2-en-1-one Structure

2-[[tert-butyl(...

~%

2-hydroxy-2-(hydroxymethyl)cyclopent-4-ene-1,3-dione Structure

2-hydroxy-2-(hy...

ethyl 5-oxocyclopentene-1-carboxylate Structure

ethyl 5-oxocycl...

~%

2-hydroxy-2-(hydroxymethyl)cyclopent-4-ene-1,3-dione Structure

2-hydroxy-2-(hy...

cis-4,5-dihydroxy-5-[[(tert-butyldimethylsilyl)oxy]methyl]-2-cyclopentenone Structure

cis-4,5-dihydro...

~%

2-hydroxy-2-(hydroxymethyl)cyclopent-4-ene-1,3-dione Structure

2-hydroxy-2-(hy...

cis-2,3-dihydroxy-2-[[(tert-butyldimethylsilyl)oxy]methyl]cyclopentanone Structure

cis-2,3-dihydro...

~%

2-hydroxy-2-(hydroxymethyl)cyclopent-4-ene-1,3-dione Structure

2-hydroxy-2-(hy...

6-carbethoxy-1,4-dioxaspiro[4.4]non-6-ene Structure

6-carbethoxy-1,...

~%

ethyl 5-oxocyclopentene-1-carboxylate Structure

ethyl 5-oxocycl...

A Convenient Procedure for the Synthesis of Acetals from α??...

[Carlson, Rolf; Gautun, Hanna; Westerlund, Andreas Advanced Synthesis and Catalysis, 2002 , vol. 344, # 1 p. 57 - 60]

Zinc-Mediated Highly α-Regioselective 1, 4-Addition of Chalc...

[Hanessian, Stephen; Mainetti, Emily; Lecomte, Fabien Organic Letters, 2006 , vol. 8, # 18 p. 4047 - 4049]

Highly Selective Methods for α-Alkenylation and α-Arylation ...

[Negishi, Ei-ichi; Akiyoshi, Kazunari Chemistry Letters, 1987 , p. 1007 - 1010]