Stereoselective Deoxygenation of <i>myo</i>-Inositol Monotosylates with Lithium Triethylborohydride

Yu, Jin‐Quan; Spencer, Jonathan B.

doi:10.1021/jo960413b

Cited by 11 publications

(9 citation statements)

References 19 publications

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“…Verbindung 7 wurde kiirzlich in racemischer Form aus myo-Inositol synthetisiert (Schema 7). [17] Unter den gleichen Bedingungen wurden die Vinylacetale 10 und 13 umgesetzt (Schema 8), die aus Methyl-fl-D-galactopyranosid und Methyl-a-D-mannopyranosid hergestellt wurden Tabelle 1. Physikalische und spektroskopische Daten der Verbindungen 2, 4, 5, 7-9, 11, 12 und 14 [a].…”

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Neuartiger Ringschluß von Hex‐5‐enpyranosiden zu carbocyclischen Verbindungen

1997

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Neuartiger Ringschluß von Hex‐5‐enpyranosiden zu carbocyclischen Verbindungen

1997

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“…Epoxide formation occurred with trans-diol tosylates, 7a,b whereas ring contraction,7c tosylate displacement by hydride,7d and a [1,2]-hydride shift 7d were observed with other substrates. More recently, deoxygenation of inositol monotosylates with LTBH was found to involve a [1,2]-hydride shift and stereoselective reduction of the derived ketone with retention of configuration …”

Section: Introductionmentioning

confidence: 99%

Deoxygenative [1,2]-Hydride Shift Rearrangements in Nucleoside and Sugar Chemistry: Analogy with the [1,2]-Electron Shift in the Deoxygenation of Ribonucleotides by Ribonucleotide Reductases¹

et al. 2007

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A variant of the semipinacol rearrangement that was observed in our laboratory has been applied to the synthesis of several furanose and pyranose derivatives. The process consists of an "orchestrated" [1,2]-hydride shift with departure of a leaving group from the opposite face. Transient formation of a C=O group is followed by rapid transfer of a hydride-equivalent from the same face from which the leaving group departed, which results in double inversion of stereochemistry at the two vicinal carbon atoms. Treatment of 2'-O- and 3'-O-tosyladenosine with lithium triethylborohydride in DMSO/THF gave the respective 2'- and 3'-deoxynucleoside analogues with beta-D-threo configurations. Identical treatment of 5'-O-TPS-2'-O-tosyladenosine gave 9-(5-O-TPS-2-deoxy-beta-D-threo-pentofuranosyl)adenine. The same [1,2]-hydride shift and stereochemistry with the 5'-OH and 5'-O-TPS compounds demonstrated the absence of remote hydroxyl-group participation. Application of this process to other nucleoside 2'-O-tosyl derivatives gave the 2'-deoxy-threo compounds in good yields. The reaction-rate order was OTs approximately Br >> Cl for 2'-O-tosyladenosine, 2'-bromo-2'-deoxyadenosine, and 2'-chloro-2'-deoxyadenosine (all with beta-d-ribo configurations). Analogous results were obtained with mannopyranoside derivatives with either 4,6-O-benzylidene protection or a free OH group at C4. Deuterium labeling clearly defined the stereochemical course as a cis-vicinal [1,2]-hydride shift on the face opposite to the original cis OH and OTs groups followed by hydride transfer from the face opposite to the [1,2]-hydride shift. Synthetic and mechanistic considerations are discussed.

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“…The vicinal, trans-diol of (+)-8 was protected by butanedione to yield diacetal 10. 33 The stereoselective deoxygenation of myo-inositol monotosylates, developed by Yu and Spencer, 34 was applied to convert 10 to tosylate 11 followed by reduction with lithium triethylborohydride to yield deoxy-inositol 12. The axial hydroxyl group was transformed to a triflate and replaced with an azido group to form 13 in 70% yield over the two steps.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Asymmetric Synthesis of Nabscessin A from Inositol and d-Camphor

Wang

Feng

et al. 2020

J. Org. Chem.

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An enantiomer of nabscessin A (1), an aminocyclitol amide with antimicrobial activity, was synthesized from myo-inositol and dimethyl d-camphor acetal in 14 steps. Formal synthesis of natural nabscessin A was also achieved through the new approach to access both enantiomers of 4,5-di-O-benzyl-myo-inositol, derived from the same set of starting materials. This synthesis features utilizations of the existing framework of myo-inositol and a regioselective esterification.

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Stereoselective Deoxygenation of myo-Inositol Monotosylates with Lithium Triethylborohydride

Cited by 11 publications

References 19 publications

Neuartiger Ringschluß von Hex‐5‐enpyranosiden zu carbocyclischen Verbindungen

Neuartiger Ringschluß von Hex‐5‐enpyranosiden zu carbocyclischen Verbindungen

Deoxygenative [1,2]-Hydride Shift Rearrangements in Nucleoside and Sugar Chemistry: Analogy with the [1,2]-Electron Shift in the Deoxygenation of Ribonucleotides by Ribonucleotide Reductases¹

Asymmetric Synthesis of Nabscessin A from Inositol and d-Camphor

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Stereoselective Deoxygenation of myo-Inositol Monotosylates with Lithium Triethylborohydride

Cited by 11 publications

References 19 publications

Neuartiger Ringschluß von Hex‐5‐enpyranosiden zu carbocyclischen Verbindungen

Neuartiger Ringschluß von Hex‐5‐enpyranosiden zu carbocyclischen Verbindungen

Deoxygenative [1,2]-Hydride Shift Rearrangements in Nucleoside and Sugar Chemistry: Analogy with the [1,2]-Electron Shift in the Deoxygenation of Ribonucleotides by Ribonucleotide Reductases1

Asymmetric Synthesis of Nabscessin A from Inositol and d-Camphor

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Deoxygenative [1,2]-Hydride Shift Rearrangements in Nucleoside and Sugar Chemistry: Analogy with the [1,2]-Electron Shift in the Deoxygenation of Ribonucleotides by Ribonucleotide Reductases¹