Stereoselective synthesis of 1,4-dideoxy-1,4-imino-d-allitol and formal synthesis of (2S,3R,4S)-3,4-dihydroxyproline

Madhan, A.; Rao, B. Venkateswara

doi:10.1016/s0040-4039(03)01366-2

Cited by 39 publications

(1 citation statement)

References 27 publications

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“…In an interesting work by Rao and co-workers [ 54 ] a Grignard reaction was employed to design the diene with desired stereochemistry for the synthesis of 1,4-dideoxy-1,4-imino-D-allitol ( 29 ) and the formal synthesis of (2 S ,3 R ,4 S )-3,4-dihydroxyproline ( 30 ) ( Scheme 5 ). According to their methodology, ( R )-2,3- O -isopropylidene-D-glyceraldehyde ( 24 ) was treated in a one-pot reaction with benzylamine and then subjected to Grignard addition with vinylmagnesium bromide to provide the alkene 25 as a single diastereomer.…”

Section: Reviewmentioning

confidence: 99%

Metathesis access to monocyclic iminocyclitol-based therapeutic agents

Drăguţan¹,

Drăguţan²,

Mitan³

et al. 2011

Beilstein J. Org. Chem.

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SummaryBy focusing on recent developments on natural and non-natural azasugars (iminocyclitols), this review bolsters the case for the role of olefin metathesis reactions (RCM, CM) as key transformations in the multistep syntheses of pyrrolidine-, piperidine- and azepane-based iminocyclitols, as important therapeutic agents against a range of common diseases and as tools for studying metabolic disorders. Considerable improvements brought about by introduction of one or more metathesis steps are outlined, with emphasis on the exquisite steric control and atom-economical outcome of the overall process. The comparative performance of several established metathesis catalysts is also highlighted.

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Section: Reviewmentioning

confidence: 99%

Metathesis access to monocyclic iminocyclitol-based therapeutic agents

Drăguţan¹,

Drăguţan²,

Mitan³

et al. 2011

Beilstein J. Org. Chem.

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Olefin Ring‐Closing Metathesis

Yet

2016

Organic Reactions

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The olefin ring‐closing metathesis reaction catalyzed by ruthenium and molybdenum complexes has been employed in the syntheses of carbocycles, heterocycles, supramolecular compounds, and in tandem metathesis reactions. Chiral ruthenium and molybdenum catalysts have provided high enantiomeric and diastereomeric excesses in ring‐closing metathesis reactions. Many of the unsuccessful medium‐ and large‐sized ring formations which were unsuccessful by traditional methods, such as the intramolecular Wittig, Horner–Wadsworth–Emmons, and Julia–Kocienski reactions, can now be formed by olefin ring‐closing metathesis reactions. Ring‐closing metathesis has been a key step and sometimes the only successful method for the synthesis of numerous natural products and drug discovery targets. The objective of this chapter is to provide an updated, comprehensive coverage of the literature of the olefin ring‐closing metathesis reaction and related processes. Key mechanistic points are summarized.

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Syntheses of Enantiomerically Pure 2‐Substituted Pyrrolidin‐3‐ones via Lithiated Alkoxyallenes – An Auxiliary‐Based Synthesis of both Enantiomers of the Antibiotic Anisomycin

Kaden

Brockmann

Reißig

2005

Helvetica Chimica Acta

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Dedicated to Professor Rolf Huisgen on the occasion of his 85th birthdayThe hydrochlorides of both enantiomers of the antibiotic anisomycin were prepared starting with the −diacetone-fructose×-substituted allene 1 and the N-Boc-protected imine precursor 2a. Addition of an excess of lithiated 1 to 2a provided a 2 : 1 mixture 3a of diastereoisomers, which were cyclized to 4a under base promotion (Scheme 2). The two diastereoisomers of 4a were separated and converted into enantiomerically pure pyrrolidin-3-ones (2R)-5a and (2S)-5a. A similar sequence yielded the N-Tos-protected compounds (2R)-5b and (2S)-5b. Compounds 5a were converted into silyl enol ethers 6 and by subsequent regio-and stereoselective hydroboration into pyrrolidine derivatives 7 (Scheme 3). Straightforward functional-group transformations led to the hydrochlorides 9 of anisomycin (Scheme 3). The (2R) series provided the hydrochloride (2R)-9 of the natural occurring enantiomer, whereas the (2S) series furnished the antipode (2S)-9. The overall sequence to the natural product involved ten steps with eight purified intermediates and afforded an overall yield of 8%. Our stereochemically divergent approach to this type of hydroxylated pyrrolidines is highly flexible and should easily allow preparation of many analogues.Introduction. ± A variety of interesting biologically active natural products contain configurationally defined pyrrolidine substructures among which many bear 3-hydroxy substituents or related functional groups. As a consequence, their synthesis and that of analogues has attracted much attention 1 ). Typical examples of these pyrrolidinol derivatives are ()-preussin, (À)-detoxinine, and (À)-anisomycin (Scheme 1), which display interesting biological activities. We have earlier prepared (À)-preussin and (À)-detoxinine by constructing their pyrrolidine core A from alkoxyallenes B and Nprotected imines C. Lithiation of B at C(1) and addition of these strong nucleophiles to imines C followed by ring closure of the primary adducts provided the required dihydropyrrole derivatives A by an efficient [3 2] cyclization mode [2]. Whereas the stereochemical control of the synthesis of (À)-detoxinine was easily achieved with a chiral side chain R 1 of imine C [3], the preparation of (À)-preussin exploited a chiral auxiliary R 2 at the alkoxyallene building block B. In this synthesis [4], the most-difficult problem was control of the configuration at C(5) of the pyrrolidine. In this report, we demonstrate that a suitable auxiliary also allows the synthesis of both enantiomers of anisomycin.(À)-Anisomycin ± a compound with a 4-methoxyphenyl substituent ± is a secondary metabolite of streptomyces species (Streptomyces grisoleaus and S. roseochromo-

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Stereoselective synthesis of 1,4-dideoxy-1,4-imino-d-allitol and formal synthesis of (2S,3R,4S)-3,4-dihydroxyproline

Cited by 39 publications

References 27 publications

Metathesis access to monocyclic iminocyclitol-based therapeutic agents

Metathesis access to monocyclic iminocyclitol-based therapeutic agents

Olefin Ring‐Closing Metathesis

Syntheses of Enantiomerically Pure 2‐Substituted Pyrrolidin‐3‐ones via Lithiated Alkoxyallenes – An Auxiliary‐Based Synthesis of both Enantiomers of the Antibiotic Anisomycin

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