Metallorganische diazoverbindungen XI. 1,3-Dipolare cycloadditionen metallorganischer diazoalkane LnMC(N2)R mit acetylendicarbonsäuredimethylester

Grüning, Rainer; Lorberth, Jörg

doi:10.1016/s0022-328x(00)93226-1

Cited by 14 publications

(1 citation statement)

References 21 publications

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“…Furthermore, compounds 7 and 8 contain an extra pnictogen atom, that is, antimony at the bridgehead position. Considering such diaza analogues (Figure A), to the best of our knowledge, no example has yet been structurally characterized, although these compounds have been considered as intermediates in the synthesis of substituted quinolines . Similarly, heterocycles containing two mutually connected heavier pnictogens are extremely rare, and as yet comprise only two examples, both of them combining nitrogen and phosphorus atoms, and one of them being further stabilized by coordination of a metal center (Figure C) .…”

Section: Resultsmentioning

confidence: 99%

Hetero Diels–Alder Reactions of Masked Dienes Containing Heavy Group 15 Elements

Kořenková

Kremláček

Hejda

et al. 2020

Chemistry A European J

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Treatment of N,C,N-chelated organopnictogen(I) compounds ArE (1-3)( Ar = 2,6-(RN=CH) 2 C 6 H 3 ,E /R = As/Dmp (1), Sb/tBu (2), and Bi/tBu (3), where Dmp = 2,6-Me 2 C 6 H 3 ) with various electron-deficient alkynes RCCR' (R/R' = CO 2 Me (DMAD), R/R' = H/CO 2 Me, or R/R' = NC 5 F 4 )a ffords different types of heterocyclic compounds. In these reactions, 1-3 act as hidden dienes and participate in hetero-Diels-Alder (DA) reactions, af eature that has been only rarely reported for heavierp nictogen compounds. In this way,r eactions of 1 furnished the set of 1-arsanaphthalenes 4-6.T he mostl ikely mechanism involves two steps, that is, an arsa-DA reaction giving a1 -arsa-1,4-dihydro-iminonaphthalene, followed by CH!NH proton migration. In contrast, this reaction se-quence terminates at the first step in the case of the antimony analogue 2,t hus giving the 1-stiba-1,4-dihydro-iminonaphthalenes 7 and 8.R eactions of the bismuth congener 3 gave one of two products depending on the alkyne used. Reactiono f3 with DMAD gave 1-bisma-1,4-dihydro-iminonaphthalene 9,w hilst its reactionw ith two equivalents of HCC(CO 2 Me) gave bismacyclohexadiene (10). All compounds have been characterized by NMR, IR, and Raman spectroscopiesa nd X-ray diffraction analysis. The experimental data were complemented by ac omputational study,i ncludingadescription of the reaction profileso ft he hetero-DA reactions and an assessment of the aromaticitieso ft he heterocyclic naphthalene derivatives. Scheme1.Example of theb isma-DA reaction producing bisma[2.2.2]bicyclooctadiene (A). Formation of 1-arsanaphthalenethrough the intermediate (INT)f ormed by arsa-DA reaction (B); Dip = 2,6-(iPr) 2 C 6 H 3 .[a] Ing.

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Section: Resultsmentioning

confidence: 99%

Hetero Diels–Alder Reactions of Masked Dienes Containing Heavy Group 15 Elements

Kořenková

Kremláček

Hejda

et al. 2020

Chemistry A European J

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ChemInform Abstract: ORGANOMETALLIC DIAZO COMPOUNDS. XI. 1,3‐DIPOLAR CYCLOADDITIONS OF ORGANOMETALLIC LNMC(N2)R TO DIMETHYL ACETYLENEDICARBOXYLATE

Gruening¹,

Lorberth²

1977

Chemischer Informationsdienst

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Teil‐ und perfluorierte Thioketone und Thioaldehyde Chemische Speicherung, in‐situ‐Freisetzung und ungewöhnliche 1,3‐dipolarophile Reaktivität gegenüber Bis(trimethylstannyl)diazomethan (BTSD) und C,N‐Bis(triisopropylsilyl)nitrilimin (NI)

1995

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Partially and Perfluorinated Thioketones and Thioaldehydes: Chemical Storage, In Situ Generation and Surprising Reactivity towards Bis(trimethylstanny1)-diazomethane (BTSD) and C,N-Bis(triisopropylsily1)nitrilimine (NI)The hetero-Diels-Alder anthracene adducts la-d are synthesized in a one-pot reaction from the corresponding partially and perfluorinated carbonyl compounds in good yields. By their thermolysis in solution in presence of BTSD or NI the 1,3-dipolar 1:l cycloadducts 12a, d, 14a, b, d are obtained without any detectable by-products. The method can be of wide applicability predominantly for any aliphatic CS-unsaturated species, which are not accessible in substance due to tendency towards polymerisation, but can be stabilized as anthracene adducts. Other 1,3-dipolar cycloaddition products of BTSD and NI are obtained from reaction with isolable hexafluorothioacetone (6f) or bis(trifluoromethy1)sulfine (7f). Comparative studies were carried out with hexafluoroacetone (8). 12a, d, e, 13 are consecutive products from a 1,2-metallotropic migration of the primary addition compounds. 14a, b, d, 15, 16 are useful thiadiazolines with respect to the synthesis of active substances because of their seldom found peripheral functionality. Desilylation was achieved by fluoride support. An X-ray structure determination of 12a and 14d was carried out. In addition trifluoromethylsulfine (7c) was trapped at low temperatures. It dimerizes at ambient temperature to unsymmetrical 1,2-dithietane 11.

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Metallorganische diazoverbindungen XI. 1,3-Dipolare cycloadditionen metallorganischer diazoalkane LnMC(N2)R mit acetylendicarbonsäuredimethylester

Cited by 14 publications

References 21 publications

Hetero Diels–Alder Reactions of Masked Dienes Containing Heavy Group 15 Elements

Hetero Diels–Alder Reactions of Masked Dienes Containing Heavy Group 15 Elements

ChemInform Abstract: ORGANOMETALLIC DIAZO COMPOUNDS. XI. 1,3‐DIPOLAR CYCLOADDITIONS OF ORGANOMETALLIC LNMC(N2)R TO DIMETHYL ACETYLENEDICARBOXYLATE

Teil‐ und perfluorierte Thioketone und Thioaldehyde Chemische Speicherung, in‐situ‐Freisetzung und ungewöhnliche 1,3‐dipolarophile Reaktivität gegenüber Bis(trimethylstannyl)diazomethan (BTSD) und C,N‐Bis(triisopropylsilyl)nitrilimin (NI)

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