Synthesis of Mixed Sequence Borane Phosphonate DNA

McCuen, Heather Brummel; Noe, Mary; Sierzchala, Agnieszka; Higson, and Adrian P.; Caruthers, Marvin H.

doi:10.1021/ja061757e

Cited by 31 publications

(34 citation statements)

References 9 publications

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“…We hope that such unparalleled versatility of these synthons will find broad usage in organophosphorous reaction schemes as well as further studies into gaining better understanding of the structure and bonding in these compounds.The synthetic methodology for preparing bpDNA oligomers we have developed previously 27 has a two-fold benefit in enabling the versatile method of DNA modification described here. Firstly the ability to prepare 25-30mer bpDNA, having all four nucleoside bases, in essentially quantitative yield far exceeds any previously reported procedure16,37,38,39,40,41 . Thus we are able to produce modified oligomers derived from boranephosphonates of lengths that are necessary for applications such as DNA based materials, antisense agents and sensors.…”

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confidence: 81%

Oxidative Substitution of Boranephosphonate Diesters as a Route to Post-synthetically Modified DNA

et al. 2015

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The introduction of modifications into oligonucleotides is important for a large number of applications in the nucleic acids field. However, the method of solid-phase DNA synthesis presents significant challenges for incorporating many useful modifications that are unstable to the conditions for preparing synthetic DNA. Here we report that boranephosphonate diesters undergo facile nucleophilic substitution in a stereospecific manner upon activation by iodine. We have subsequently used this reactivity to post-synthetically introduce modifications including azides and fluorophores into DNA by first synthesizing boranephosphonate-linked 2'-deoxyoligonucleotides and then treating these oligomers with iodine and various nucleophiles. In addition, we show that this reaction is an attractive method for preparing stereodefined phosphorus-modified oligonucleotides. We have also examined the mechanism of this reaction and show that it proceeds via an iodophosphate intermediate. Beyond nucleic acids synthesis, due to the ubiquity of phosphate derivatives in natural compounds and therapeutics, this stereospecific reaction has many potential applications in organophosphorus chemistry.

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confidence: 81%

Oxidative Substitution of Boranephosphonate Diesters as a Route to Post-synthetically Modified DNA

et al. 2015

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“…Nucleic acid boranophosphates were pioneered by Shaw,11 and they are receiving increasing attention for therapeutics and diagnostics 12-14. Thiophosphates are well known to display altered interactions with other species, including metals 15.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of boranoate, selenoate, and thioate analogs of AZTp4A and Ap4A

et al. 2009

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We report efficient, one-flask procedures for the synthesis of a family of fourteen analogs of AZTp 4 A and Ap 4 A containing BH 3 , S, or Se, along with two bisphosphonate analogs of Ap 4 A. These compounds should slow unwanted enzymatic hydrolysis and have the potential to create unique binding interactions in biochemical and structural studies of the excision reaction responsible for resistance of HIV-1 to AZT, as well as assist in drug design.

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“…We have reported an alternative method, adapted from RNA synthesis, that uses 5'- O -silyl 2'-deoxynucleosides 3'-phosphoramidites containing N -trimethoxytrityl (TMTr)-protected nucleobases [43]. These protecting groups were found to be stable toward reduction by borane.…”

Section: Dna Containing Stable Complexes Of P (Iii) With Lewis Acidsmentioning

confidence: 99%

Synthesis of DNA/RNA and Their Analogs via Phosphoramidite and H-Phosphonate Chemistries

Roy

Caruthers

2013

Molecules

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Abstract:The chemical synthesis of DNA and RNA is universally carried out using nucleoside phosphoramidites or H-phosphonates as synthons. This review focuses on the phosphorus chemistry behind these synthons and how it has been developed to generate procedures whereby yields per condensation approach 100% with very few side products. Additionally the synthesis and properties of certain DNA and RNA analogs that are modified at phosphorus will also be discussed. These analogs include boranephosphonates, metallophosphonates, and alkylboranephosphines.

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Synthesis of Mixed Sequence Borane Phosphonate DNA

Cited by 31 publications

References 9 publications

Oxidative Substitution of Boranephosphonate Diesters as a Route to Post-synthetically Modified DNA

Oxidative Substitution of Boranephosphonate Diesters as a Route to Post-synthetically Modified DNA

Synthesis of boranoate, selenoate, and thioate analogs of AZTp4A and Ap4A

Synthesis of DNA/RNA and Their Analogs via Phosphoramidite and H-Phosphonate Chemistries

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