Free radical reactions of organomercurials

Cited by 63 publications

(11 citation statements)

References 46 publications

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“…The lack of nitro compounds in the alkylmercuric bromide photolyses was, at first, surprising because photolysis of t-butylmercuric chloride in the presence of nitrite (Russell and Khanna 1985) and 5-hexenylmercuric chloride in the presence of 2-nitropropane anion (Russell and Guo 1984) had been observed to produce nitro compounds. However, a review of the SRNl chemistry of alkylmercuric halides (Barluenga and Yus 1988;Russell 1989) showed that bromides do not give as good a yield as chlorides and that the rates of electron transfer (radical anion to alkylmercuric chloride) decrease in the order tertiary>secondary>primary. Thus, it seems that production of nitroalkanes in these systems should not be as efficient as expected due to sluggish reaction rates for converting the nitroanion to nitroalkane via electron transfer.…”

Section: Alkylmercuric Bromide Photolysesmentioning

confidence: 99%

Organic Tanks Safety Program: Waste aging studies

Camaioni¹,

Samuels²,

Lenihan³

et al. 1994

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Section: Alkylmercuric Bromide Photolysesmentioning

confidence: 99%

Organic Tanks Safety Program: Waste aging studies

Camaioni¹,

Samuels²,

Lenihan³

et al. 1994

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“…Oxidative Reactions of Bromomercurials. Reduction of halomercurials R−HgX with NaBH 4 proceeds via a radical mechanism, as evidenced, for instance, by the addition to methyl acrylate. ,, Alternatively, the incipient radical can be trapped by oxygen bubbled through the reaction mixture to generate peroxide R−OOH, which is further reduced by the hydride present to the corresponding alcohol. 31d,− Application of this protocol (O 2 , NaBH 4 , DMF, rt, 15 min) to the bromomercurial 8 (Scheme ) produced a mixture of the fully reduced alcohol 12 (2%), the expected diol 28 (49%), and the lactol 11 (37%). Formation of the latter byproduct demonstrates that removal of the HgBr group is faster than the reduction of the aldehyde moiety.…”

Section: Resultsmentioning

confidence: 99%

An Approach toward the Triquinane-Type Skeleton via Reagent-Controlled Skeletal Rearrangements. A Facile Method for Protection−Deprotection of Organomercurials, Tuning the Selectivity of Wagner−Meerwein Migrations, and a New Route to Annulated Lactones

et al. 1998

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Nonlinear triquinane-type building blocks have been synthesized using three strategic steps, namely, (1) Hg(2+)-mediated opening of a cyclopropane ring involving a skeletal rearrangement (3 --> 8), (2) an intramolecular organometallic addition across a C=O bond triggered by activation of the C-HgX group by means of Me(3)CuLi(2) (14 --> 26), and (3) selective, reagent-controlled skeletal rearrangements (43 --> 47 with Tl(3+) or Hg(2+); 43 --> 51 + 52 with Pd(2+); 44 --> 47 with Pd(2+)). A new method for protection/deprotection of organomercurials has been developed, which allows selective reduction of a carbonyl group with NaBH(4) and other hydrides (8 --> 14 --> 16 --> 20) and Tebbe methylenation (14 --> 31 --> 32). Oxidative demercuration (8 --> 11 + 28) and Pd(2+)-catalyzed carbonylation of organomercurials (20 --> 53) allowed syntheses of gamma- and delta-lactones.

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“…τ 1/2 (5% in CDCl 3 ): 7 min. 1 H NMR (CDCl 3 , 400 MHz) δ 1.18 (qd, 2H, 3 J HH = 7.7 Hz, 3 J HH = 3.7 Hz, CH 2 ) ; 1.30 (td, 2H, 3 J HH = 7.7 Hz, 4 J HH = 3.3 Hz, CH 3 ) ; 17.1 (tq, 1H, 3 J HH = 3.7 Hz, 4 J HH = 3.3 Hz, 1 J HgH = 2339.8 Hz (d), HgH). 13 C NMR (CDCl 3 , 100 MHz) δ 13.4 (t, 1 J CH = 127.7 Hz, 2 J HgC = 36.3 Hz (d), CH 3 ) ; 32.6 (q, 1 J CH = 131.3 Hz, 1 J HgC = 831.2 Hz (d), CH 2 ).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Synthesis, High-Resolution Millimeter-Wave Spectroscopy, and Ab Initio Calculations of Ethylmercury Hydride

et al. 2012

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The millimeter-wave rotational spectrum of an organomercury compound, ethylmercury hydride, has been recorded and assigned for the first time. The spectroscopic study is complemented by quantum chemical calculations taking into account relativistic effects on the mercury atom. The very good agreement between theoretical and experimental molecular parameters validates the chosen ab initio method, in particular its capability to predict accurate quartic centrifugal distortion constants related to this type of compound. Estimations of the nuclear quadrupole coupling constants have less predictive power than those of the structural parameters, but are good enough to satisfy the spectroscopic needs. In addition, the orientation of the axis of the H-Hg-C bonds deduced from the experimental nuclear quadrupole coupling constants compares well with the corresponding ab initio value. From the good agreement between experimental and theoretical results, together with the observation of the six most abundant isotopes of mercury, ethylmercury hydride is unambiguously identified as the product of the chemical reaction described here, and its calculated equilibrium geometry is confirmed.

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Free radical reactions of organomercurials

Cited by 63 publications

References 46 publications

Organic Tanks Safety Program: Waste aging studies

Organic Tanks Safety Program: Waste aging studies

An Approach toward the Triquinane-Type Skeleton via Reagent-Controlled Skeletal Rearrangements. A Facile Method for Protection−Deprotection of Organomercurials, Tuning the Selectivity of Wagner−Meerwein Migrations, and a New Route to Annulated Lactones

Synthesis, High-Resolution Millimeter-Wave Spectroscopy, and Ab Initio Calculations of Ethylmercury Hydride

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