Synthesis of annulated furanoses by free-radical cyclization of haloalkenes derived from diacetone glucose

Marco‐Contelles, José; Martinez‐Grau, A.; Martı́nez-Ripoll, M.; Cano, H.; Foces‐Foces, C.

doi:10.1021/jo00027a076

Cited by 13 publications

(2 citation statements)

References 5 publications

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“…To avoid the side reactions, starting material was highly diluted, and Bn 3 SnH and AIBN were added dropwise slowly (Experimental Section). As previously reported, , the radical reaction proceeded in the 6- exo cyclization mode to afford the sole product 14 in 60% yield. Meanwhile 1D NOE experiments proved that the configuration of C8′ was R stereochemistry.…”

Section: Resultssupporting

confidence: 59%

Synthesis of 2′,4′-Propylene-Bridged (Carba-ENA) Thymidine and Its Analogues: The Engineering of Electrostatic and Steric Effects at the Bottom of the Minor Groove for Nuclease and Thermodynamic Stabilities and Elicitation of RNase H

Liu

Karimiahmadabadi

et al. 2010

J. Org. Chem.

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2',4'-Propylene-bridged thymidine (carba-ENA-T) and five 8'-Me/NH(2)/OH modified carba-ENA-T analogues have been prepared through intramolecular radical addition to C═N of the tethered oxime-ether. These carba-ENA nucleosides have been subsequently incorporated into 15mer oligodeoxynucleotides (AON), and their affinity toward cDNA and RNA, nuclease resistance, and RNase H recruitment capability have been investigated in comparison with those of the native and ENA counterparts. These carba-ENAs modified AONs are highly RNA-selective since all of them led to slight thermal stabilization effect for the AON:RNA duplex, but quite large destabilization effect for the AON:DNA duplex. It was found that different C8' substituents (at the bottom of the minor groove) on carba-ENA-T only led to rather small variation of thermal stability of the AON:RNA duplexes. We, however, observed that the parent carba-ENA-T modified AONs exhibited higher nucleolytic stability than those of the ENA-T modified counterparts. The nucleolytic stability of carba-ENA-T modified AONs can be further modulated by C8' substituent to variable extents depending on not only the chemical nature but also the stereochemical orientation of the C8' substituents: Thus, (1) 8'S-Me on carba-ENA increases the nucleolytic stability but 8'R-Me leads to a decreased effect; (2) 8'R-OH on carba-ENA had little, if any, effect on nuclease resistance but 8'S-OH resulted in significantly decreased nucleolytic stability; and (3) 8'-NH(2) substituted carba-ENA leads to obvious loss in the nuclease resistance. The RNA strand in all of the carba-ENA derivatives modified AON:RNA hybrid duplexes can be digested by RNase H1 with high efficiency, even at twice the rate of those of the native and ENA modified counterpart.

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Section: Resultssupporting

confidence: 59%

Synthesis of 2′,4′-Propylene-Bridged (Carba-ENA) Thymidine and Its Analogues: The Engineering of Electrostatic and Steric Effects at the Bottom of the Minor Groove for Nuclease and Thermodynamic Stabilities and Elicitation of RNase H

Liu

Karimiahmadabadi

et al. 2010

J. Org. Chem.

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“…Nevertheless, the 6-exo cyclization is a well known procedure in the synthesis of branched chain sugars where the cyclization of hept-6-enyl radicals is accelerated by the introduction of electron-withdrawing groups in the radical acceptor. 25 Crich obtained a 1 : 1 mixture of the cyclohexanones 44 and 45 (Scheme 16), in 90% yield after cyclization of an acyclic acyl radical. 26 Redlich carried out a very interesting study on the cyclization of 7-deoxy-7-iodohept-1-enitols of the allo-, manno-, galacto-and gulo-series using tributyltin hydride.…”

Section: Bu 3 Snh-mediated 6-exo Cyclizationmentioning

confidence: 99%

Carbocycles from carbohydrates via free radical cyclizations: new synthetic approaches to glycomimetics

Martinez‐Grau¹,

Marco‐Contelles²

1998

Chem. Soc. Rev.

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Free radical cyclization of enantiomerically pure, acyclic presursors derived from carbohydrates is an excellent method for the synthesis of complex, densely functionalized chiral carbohydrate mimics ('glycomimetics'). The extent of the acyclic diastereoselection can be modulated and is closely associated with the structure, rigidity and conformational aspects of the radical precursors. General models for a rationale of the stereochemical outcome of the cyclizations are shown.

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Formation of Alkanes and Arenes by Ring‐forming Reactions

Larock

Zhang

2018

Comprehensive Organic Transformations

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Synthesis of annulated furanoses by free-radical cyclization of haloalkenes derived from diacetone glucose

Cited by 13 publications

References 5 publications

Synthesis of 2′,4′-Propylene-Bridged (Carba-ENA) Thymidine and Its Analogues: The Engineering of Electrostatic and Steric Effects at the Bottom of the Minor Groove for Nuclease and Thermodynamic Stabilities and Elicitation of RNase H

Synthesis of 2′,4′-Propylene-Bridged (Carba-ENA) Thymidine and Its Analogues: The Engineering of Electrostatic and Steric Effects at the Bottom of the Minor Groove for Nuclease and Thermodynamic Stabilities and Elicitation of RNase H

Carbocycles from carbohydrates via free radical cyclizations: new synthetic approaches to glycomimetics

Formation of Alkanes and Arenes by Ring‐forming Reactions

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