Osmium-free direct syn-dihydroxylation of alkenes

Bataille, Carole J. R.; Donohoe, Timothy J.

doi:10.1039/b923880h

Cited by 221 publications

(107 citation statements)

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“…69,70 Through the insequence routes of precursor-directed biosynthesis and semisynthesis, this work describes new avenues toward the generation of a high degree of molecular diversity within the macrocyclic dihydroxamic acid class of siderophores. Bacterial Culturing.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Unsaturated Macrocyclic Dihydroxamic Acid Siderophores Produced byShewanella putrefaciensUsing Precursor-Directed Biosynthesis

Soe

Codd

2014

ACS Chem. Biol.

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To acquire iron essential for growth, the bacterium Shewanella putrefaciens produces the macrocyclic dihydroxamic acid putrebactin (pbH2; [M + H(+)](+), m/zcalc 373.2) as its native siderophore. The assembly of pbH2 requires endogenous 1,4-diaminobutane (DB), which is produced from the ornithine decarboxylase (ODC)-catalyzed decarboxylation of l-ornithine. In this work, levels of endogenous DB were attenuated in S. putrefaciens cultures by augmenting the medium with the ODC inhibitor 1,4-diamino-2-butanone (DBO). The presence in the medium of DBO together with alternative exogenous non-native diamine substrates, (15)N2-1,4-diaminobutane ((15)N2-DB) or 1,4-diamino-2(E)-butene (E-DBE), resulted in the respective biosynthesis of (15)N-labeled pbH2 ((15)N4-pbH2; [M + H(+)](+), m/zcalc 377.2, m/zobs 377.2) or the unsaturated pbH2 variant, named here: E,E-putrebactene (E,E-pbeH2; [M + H(+)](+), m/zcalc 369.2, m/zobs 369.2). In the latter system, remaining endogenous DB resulted in the parallel biosynthesis of the monounsaturated DB-E-DBE hybrid, E-putrebactene (E-pbxH2; [M + H(+)](+), m/zcalc 371.2, m/zobs 371.2). These are the first identified unsaturated macrocyclic dihydroxamic acid siderophores. LC-MS measurements showed 1:1 complexes formed between Fe(III) and pbH2 ([Fe(pb)](+); [M](+), m/zcalc 426.1, m/zobs 426.2), (15)N4-pbH2 ([Fe((15)N4-pb)](+); [M](+), m/zcalc 430.1, m/zobs 430.1), E,E-pbeH2 ([Fe(E,E-pbe)](+); [M](+), m/zcalc 422.1, m/zobs 422.0), or E-pbxH2 ([Fe(E-pbx)](+); [M](+), m/zcalc 424.1, m/zobs 424.2). The order of the gain in siderophore-mediated Fe(III) solubility, as defined by the difference in retention time between the free ligand and the Fe(III)-loaded complex, was pbH2 (ΔtR = 8.77 min) > E-pbxH2 (ΔtR = 6.95 min) > E,E-pbeH2 (ΔtR = 6.16 min), which suggests one possible reason why nature has selected for saturated rather than unsaturated siderophores as Fe(III) solubilization agents. The potential to conduct multiple types of ex situ chemical conversions across the double bond(s) of the unsaturated macrocycles provides a new route to increased molecular diversity in this class of siderophore.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Unsaturated Macrocyclic Dihydroxamic Acid Siderophores Produced byShewanella putrefaciensUsing Precursor-Directed Biosynthesis

Soe

Codd

2014

ACS Chem. Biol.

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“…Donohoe's research group studied hydrogen-bondingdirected stereoselective dihydroxylation with OsO 4 , giving the syn,syn triol [68,69]. This process realized reverse stereoselectivity on allylic dihydroxylation with OsO 4 , against normal syn,anti selectivity following Kishi's empirical rule [70].…”

Section: First Synthesis Of (þ)-Pericosine B By Donohoementioning

confidence: 97%

Synthesis of Marine-Derived Carbasugar Pericosines

Usami

2014

Studies in Natural Products Chemistry

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“…18 Since osmium tetroxide is expensive and very toxic, alternatives to this catalyst system have been sought, 19 and dihydroxylation of a,b-unsaturated carbonyl compounds can also be performed with permanganate ions or ruthenium tetroxide. 20 Permanganate has a high oxidation potential and its use can easily lead to overoxidations or other side reactions.…”

Section: Dihydroxylation Of Ab-unsaturated Carbonyl Compoundsmentioning

confidence: 99%