Dimeric Olefins versus Amines from α-Aryl Alkyl Halides with Alkali Amides in Liquid Ammonia. Intermediate Dimeric Halides and Their Dehydrohalogenation. Imines from Amines<sup>1</sup>

Hauser, Charles R.; Brasen, Wallace R.; Skell, P. S.; Kantor, Simon W.; Brodhag, Alex E.

doi:10.1021/ja01589a043

Cited by 49 publications

(10 citation statements)

References 2 publications

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“…MeCN, t -BuCN, t -BuNC, and MesCN were obtained from commercial suppliers and dried by standard procedures. (Mes*AlH 2 ) 2 1 and H 2 NSiPh 3 were synthesized by literature methods, and H 2 NCH 2 Mes (which was originally synthesized by the reaction of MesCH 2 Cl with potassium amide) was obtained by the reduction of MesCN with LiAlH 4 . Solvents were freshly distilled under N 2 from Na/K alloy and degassed twice prior to use.…”

Section: Methodsmentioning

confidence: 99%

Reaction of the Primary Alane (2,4,6-t-Bu₃H₂C₆AlH₂)₂ with Nitriles, Isonitriles, and Primary Amines

Wehmschulte

Power

1998

Inorg. Chem.

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The reactions of the sterically encumbered primary alane (MesAlH(2))(2) (Mes = C(6)H(2)-2,4,6-t-Bu(3)) with the nitriles t-BuCN, MesCN (Mes = C(6)H(2)-2,4,6-Me(3)) or MeCN lead eventually to dimeric amido alane products in which one of the ortho t-Bu groups of the Mes ligand is metalated and the nitrile is reduced to the amide ligand N(H)CH(2)R (R = t-Bu, Mes, or Me). The compounds (R = t-Bu, 2 (cis), 3 (trans); Mes, 4 (cis), 5 (trans); Me, 6 (cis)) have been isolated and characterized spectroscopically and also by X-ray crystallography in the cases of 4 and 5. The intermediate, dimeric iminato complex [MesAl(H){&mgr;(2)-NC(H)t-Bu}](2) (1), can also be isolated under carefully controlled, mild conditions. Reaction of (MesAlH(2))(2) with the isonitrile t-BuNC affords the cyclic species {MesAlN(t-Bu)CH(2)}(2) (7) featuring a six-membered (AlNC)(2) ring which, when heated, affords the cyclometalated species (8). Recognition that the products 2-6 and 8 were derivatives of primary amides led to an investigation of synthetic approaches to these product types via the direct reaction of (MesAlH(2))(2) with some primary amines. Treatment of (MesAlH(2))(2) with H(2)NCH(2)Mes affords the dimeric amido alane [Mes(H)Al{&mgr;(2)-N(H)CH(2)Mes}](2) as a mixture of trans (9) and cis (10) isomers. Further heating of 9 and 10 affords the ortho-metalated compounds 4 and 5. The reaction of (MesAlH(2))(2) with H(2)NSiPh(3) furnishes the bis amido aluminum compound MesAl{N(H)SiPh(3)}(2) (11) and [Mes(H)Al{N(H)SiPh(3)}](2). The latter yields the dimeric imide {MesAlNSiPh(3)}(2) (12) at elevated temperature.

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Section: Methodsmentioning

confidence: 99%

Reaction of the Primary Alane (2,4,6-t-Bu₃H₂C₆AlH₂)₂ with Nitriles, Isonitriles, and Primary Amines

Wehmschulte

Power

1998

Inorg. Chem.

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“…1-phenyl-1,3-butadiene and 1,4-diphenyl-1,3-butadiene) and 1-acetoxy-1,3-butadiene did not produce the desired cyclopropanation products under these conditions. 9,9Ј-Bifluorenylidene (14) [12] and bis(9,9Ј-9H-fluorenylidene)azine (15) [13] were identified as side products in all of the cyclopropanation reactions, even though 9-diazo-9H-fluorene (2) was added slowly over the course of the reaction.…”

Section: Resultsmentioning

confidence: 99%

Highly Regio‐ and Diastereoselective Chromium(0)‐Catalysed Cyclopropanation of 1‐Alkoxy‐1,3‐dienes with Diazo Compounds

Hahn¹,

Nieger²,

Dötz³

2004

Eur J Org Chem

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Pentacarbonyl(η 2 -cis-cyclooctene)chromium(0) (1) is an efficient catalyst for diazo decomposition and selective [2+1]-cycloaddition reactions of the resulting carbene intermediates with electron-rich dienes. The cyclopropanation of 1-alkoxy-1,3-butadienes 4−8 with 9-diazo-9H-fluorene (2) yields vinylspirocyclopropanes 9−13 in good to excellent yields, as single regioisomers arising from carbene transfer to

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“…186°C (ref. [12] 185Ϫ187°C), R f ϭ 0. Reaction of 1 with Styrene: Reaction of 3 mmol 1 (0.57 g) with 3 mmol styrene (0.31 g) in the presence of 2 (0.02 g, 0.06 mmol, 2 mol%) gave 0.20 g of 7 (0.75 mmol, 25%) and 0.37 g of azine 10 (1.04 mmol, 69% based on 1) after work-up according to procedure B (eluent: petroleum ether/diethyl ether, 5:1).…”

Section: -Methoxy-2-methylspiro[cyclopropane-19ј-[9h]fluorene] (4)mentioning

confidence: 99%

Chromium Complex Catalyzed Synthesis of Spirocyclopropanes from Diaryl Diazo Compounds – Direct NMR-Spectroscopic Observation of a Carbene Complex Intermediate

Pfeiffer

Nieger

Dötz³

1998

Eur. J. Org. Chem.

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Dimeric Olefins versus Amines from α-Aryl Alkyl Halides with Alkali Amides in Liquid Ammonia. Intermediate Dimeric Halides and Their Dehydrohalogenation. Imines from Amines¹

Cited by 49 publications

References 2 publications

Reaction of the Primary Alane (2,4,6-t-Bu₃H₂C₆AlH₂)₂ with Nitriles, Isonitriles, and Primary Amines

Reaction of the Primary Alane (2,4,6-t-Bu₃H₂C₆AlH₂)₂ with Nitriles, Isonitriles, and Primary Amines

Highly Regio‐ and Diastereoselective Chromium(0)‐Catalysed Cyclopropanation of 1‐Alkoxy‐1,3‐dienes with Diazo Compounds

Chromium Complex Catalyzed Synthesis of Spirocyclopropanes from Diaryl Diazo Compounds – Direct NMR-Spectroscopic Observation of a Carbene Complex Intermediate

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Dimeric Olefins versus Amines from α-Aryl Alkyl Halides with Alkali Amides in Liquid Ammonia. Intermediate Dimeric Halides and Their Dehydrohalogenation. Imines from Amines1

Cited by 49 publications

References 2 publications

Reaction of the Primary Alane (2,4,6-t-Bu3H2C6AlH2)2 with Nitriles, Isonitriles, and Primary Amines

Reaction of the Primary Alane (2,4,6-t-Bu3H2C6AlH2)2 with Nitriles, Isonitriles, and Primary Amines

Highly Regio‐ and Diastereoselective Chromium(0)‐Catalysed Cyclopropanation of 1‐Alkoxy‐1,3‐dienes with Diazo Compounds

Chromium Complex Catalyzed Synthesis of Spirocyclopropanes from Diaryl Diazo Compounds – Direct NMR-Spectroscopic Observation of a Carbene Complex Intermediate

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Dimeric Olefins versus Amines from α-Aryl Alkyl Halides with Alkali Amides in Liquid Ammonia. Intermediate Dimeric Halides and Their Dehydrohalogenation. Imines from Amines¹

Reaction of the Primary Alane (2,4,6-t-Bu₃H₂C₆AlH₂)₂ with Nitriles, Isonitriles, and Primary Amines

Reaction of the Primary Alane (2,4,6-t-Bu₃H₂C₆AlH₂)₂ with Nitriles, Isonitriles, and Primary Amines