Competing .beta.-fragmentation in regeneration of alcohols from arenesulfonates with arene anion radicals

Closson, W. D.; Ganson, J. R.; Rhee, Sung W.; Quaal, K. S.

doi:10.1021/jo00133a048

Cited by 6 publications

(1 citation statement)

References 3 publications

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“…The possibility of consecutive SET-mediated homolytic cleavage of each carbon−oxygen bond also was considered 18b, However, analogous treatment of ditosylates gave diols,28a presumably via competitive sulfur−oxygen bond cleavage . We recently noted efficient removal of O- tosyl groups from the sugar , and halogens from the heterocycle 31 of purine nucleosides with sodium naphthalenide.…”

Section: Resultsmentioning

confidence: 99%

Nucleic Acid Related Compounds. 105. Synthesis of 2‘,3‘-Didehydro-2‘,3‘-dideoxynucleosides from Ribonucleoside Cyclic 2‘,3‘-(Sulfates or Phosphates) or 2‘,3‘-Dimesylates via Reductive Elimination with Sodium Naphthalenide¹

1998

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Treatment of purine ribonucleosides with thionyl fluoride resulted in formation of cyclic 2',3'-sulfite esters. Acetylation of the 5'-hydroxy group and Sharpless oxidation (NaIO(4)/RuCl(3)) gave the cyclic 2',3'-sulfate ester derivatives. Treatment of 5'-O-silyl-protected ribonucleosides with thionyl chloride followed by oxidation gave an alternative route to the cyclic 2',3'-sulfates. Reductive elimination with sodium naphthalenide (THF/-50 degrees C) gave the 2',3'-unsaturated nucleosides. Parallel treatment of adenosine cyclic 2',3'-phosphate gave the 2',3'-olefin. The adenine, hypoxanthine, and 2-amino-6-methoxypurine 2',3'-didehydro-2',3'-dideoxynucleosides were prepared efficiently (40-60% overall yields of crystalline, analytically pure products; 3-5 steps, some combined into one-flask procedures) by treatment of 5'-O-protected 2',3'-di-O-mesylribonucleosides with sodium naphthalenide. Reactions were performed at or below ambient temperature with readily available reagents and standard laboratory conditions.

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Section: Resultsmentioning

confidence: 99%

Nucleic Acid Related Compounds. 105. Synthesis of 2‘,3‘-Didehydro-2‘,3‘-dideoxynucleosides from Ribonucleoside Cyclic 2‘,3‘-(Sulfates or Phosphates) or 2‘,3‘-Dimesylates via Reductive Elimination with Sodium Naphthalenide¹

1998

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Chemical and spectroscopical evidence for an electron‐transfer mechanism in the reaction of arenesulfonyl chlorides with anions

et al. 1989

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The reaction of amide and amidate anions 2 with ptoluenesulfonyl chloride (1) under Merent reaction conditions gives rise to the total or prrrtial reduction of the acyl halide to p-toluenesulfiaic acid (5) and acylatioo compounds in variable amounts depending on the crowding at the anionic center. This indicates that a SingIe-Electron Transfer (SET) mechanism is involved in the reactions of 1 with anions. Unpaired electron species are detected by RTR in the course of the reactions.It is well-established that sulfur-substituted aromatic rings such as aryl sulfones 'I, arenesulfonates 21, or arenesulfonamides 3, are able to accept one electron under thermal or photochemical conditions when allowed to react with anions or other chemical and electrochemical electron sources. By contrast, the behavior of arenesulfonyl chlorides as single-electron acceptors, in spite of their extended use in organic synthesis, has not been investigated so far although they should be expected to accept a single electron from anions as efficiently or even more than the above mentioned sulfurcontaining groups. Arenesulfonyl chlorides are reduced by usual reductors (hydride or sullite anions) with great ease and also by anions such as acetylide, enolate, sulfide, mercaptide, thiosulfate, cyanide, dithionite, arsenite, iodide, and dithi~carbonate~' in reactions that have not been investigated in depth from a mechanistic point of view.For these reasons, we decided to investigate the reactivity of ptoluenesulfonyl chloride (1) with nucleophiles NueM@ (2) such as amide and amidate anions, species that might behave alternatively as two-electron or single-electron donors6'.The reaction of nucleophiles 2 with p-toluenesulfonyl chloride under different reaction conditions gave rise to total or partial reScheme 1 ~-C H~C~H~S O~C I

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Carbonylmetallates—A Special Family of Nucleophiles in Aromatic and Vinylic Substitution Reactions

Sazonov

Beletskaya

2016

Chemistry A European J

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Carbonylmetallates, [M(CO)(n)L](-), anionic transition-metal carbonyl complexes, represent a large family of metal-centered nucleophiles, and studying carbonylmetallates allows us to understand the differences in the behavior of the metal-centered complexes versus heteroatom-based nucleophiles. The mechanisms of carbonylmetallate reactions with aryl- and alkenyl halides have been examined by employing radical and, especially, carbanion trapping techniques. Carbonylmetallates show a marked preference for halogenophilic attack, and nucleophilic substitution with carbonylmetallates is often not a direct process, but proceeds through the initial attack at halogen with subsequent coupling of carbanion and HalM(CO)(n)L intermediates. Factors governing the competition between the halogenophilic and more common "carbophilic" reaction pathways, as well as the means of predicting the actual course of reaction are discussed. The review also considers other aspects of carbonylmetallate reactivity, including ion-pairing effects, radical-mediated nucleophilic substitution pathways, and the carbonylmetallate nucleophilicity scale in the reactions with π-electrophiles.

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Competing .beta.-fragmentation in regeneration of alcohols from arenesulfonates with arene anion radicals

Abstract: The same procedure as above was used with 11.5 mL of Ac20, 2.5 mL of oxide-free HN03, and a solution of 2.0 g of the amine hydrochloride in 2 mL of AcOH. A workup as above gave 0.51 g of dimethylnitramine as a first crop. Further concentration gave another 0.21 g (total yield 55%).

Cited by 6 publications

References 3 publications

Nucleic Acid Related Compounds. 105. Synthesis of 2‘,3‘-Didehydro-2‘,3‘-dideoxynucleosides from Ribonucleoside Cyclic 2‘,3‘-(Sulfates or Phosphates) or 2‘,3‘-Dimesylates via Reductive Elimination with Sodium Naphthalenide¹

Nucleic Acid Related Compounds. 105. Synthesis of 2‘,3‘-Didehydro-2‘,3‘-dideoxynucleosides from Ribonucleoside Cyclic 2‘,3‘-(Sulfates or Phosphates) or 2‘,3‘-Dimesylates via Reductive Elimination with Sodium Naphthalenide¹

Chemical and spectroscopical evidence for an electron‐transfer mechanism in the reaction of arenesulfonyl chlorides with anions

Carbonylmetallates—A Special Family of Nucleophiles in Aromatic and Vinylic Substitution Reactions

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Competing .beta.-fragmentation in regeneration of alcohols from arenesulfonates with arene anion radicals

Abstract: The same procedure as above was used with 11.5 mL of Ac20, 2.5 mL of oxide-free HN03, and a solution of 2.0 g of the amine hydrochloride in 2 mL of AcOH. A workup as above gave 0.51 g of dimethylnitramine as a first crop. Further concentration gave another 0.21 g (total yield 55%).

Cited by 6 publications

References 3 publications

Nucleic Acid Related Compounds. 105. Synthesis of 2‘,3‘-Didehydro-2‘,3‘-dideoxynucleosides from Ribonucleoside Cyclic 2‘,3‘-(Sulfates or Phosphates) or 2‘,3‘-Dimesylates via Reductive Elimination with Sodium Naphthalenide1

Nucleic Acid Related Compounds. 105. Synthesis of 2‘,3‘-Didehydro-2‘,3‘-dideoxynucleosides from Ribonucleoside Cyclic 2‘,3‘-(Sulfates or Phosphates) or 2‘,3‘-Dimesylates via Reductive Elimination with Sodium Naphthalenide1

Chemical and spectroscopical evidence for an electron‐transfer mechanism in the reaction of arenesulfonyl chlorides with anions

Carbonylmetallates—A Special Family of Nucleophiles in Aromatic and Vinylic Substitution Reactions

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Nucleic Acid Related Compounds. 105. Synthesis of 2‘,3‘-Didehydro-2‘,3‘-dideoxynucleosides from Ribonucleoside Cyclic 2‘,3‘-(Sulfates or Phosphates) or 2‘,3‘-Dimesylates via Reductive Elimination with Sodium Naphthalenide¹

Nucleic Acid Related Compounds. 105. Synthesis of 2‘,3‘-Didehydro-2‘,3‘-dideoxynucleosides from Ribonucleoside Cyclic 2‘,3‘-(Sulfates or Phosphates) or 2‘,3‘-Dimesylates via Reductive Elimination with Sodium Naphthalenide¹