The synthesis of N-heterocycles using ortho-metallated primary benzylamine complexes of palladium(II) and platinum(II)

O'Sullivan, Richard D.; Parkins, A. W.

doi:10.1039/c39840001165

Cited by 47 publications

(42 citation statements)

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“…Complexes l a and l b are expected to be more stable than their homologues with tertiary amines. Thus, the reaction between 4), where the ligands broke the 7c-olefinic bond to give the corresponding adducts. Complex 4 Cv(C0) 2 120s cm-'I is stable at room temperature when solid, although it slowly decomposes in solution.…”

Section: Resultsmentioning

confidence: 99%

Insertion of internal acetylenes into orthopalladated α-methylbenzylamine. Crystal structure of [Pd{C(Ph)C(Ph)C(Ph)C(Ph)C₆H₄CH(Me)NH₂}Br]

Vicente¹,

Saura‐Llamas²,

Arellano³

1995

J. Chem. Soc., Dalton Trans.

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The complex [Pd{C,H,CH (Me)NH,}( Me,CO),]CIO, reacted with diphenylacetylene to give [ Pd2(q5-C,Ph,),(p-q2-PhC=CPh)]. A pathway for this reaction is suggested. Species related with the postulated intermediates can be isolated starting from [{Pd[C,H,CH( Me) NH,] (p-Br)},] which reacts with disubstituted alkynes (RCECR, R = C0,Me or Ph) to afford [Pd{C(R)=C(R)C(R)=C(R)C,H,CH-(Me)NH,}Br) (R = C0,Me l a or Ph 1 b) through a double insertion of the alkyne into the Pd-C bond. Complex l a reacted with 1 equivalent of MeO,CC=CCO,Me to give the tri-insertion reaction product 2. These are the first products of alkyne insertion into a cyclopalladated primary amine. Neutral ligands, s u c h as pyridine (py) or CO, can break the Pd-n-olefinic bond in l a to give the corresponding adducts [Pd{C(R)=C(R)C(R)=C(R)C,H,CH(Me)NH,}Br(L)] ( R = C0,Me; L = py 3 or CO 4). Complexes l a and 1 b reacted with AgCIO, (1 : 1 ) in acetone to afford AgBr and [Pd{C(R)=C(R)C(R)=C(R)C,H,CH(Me)NH2}(solv)]CI0, (R = CO,Me, solv = H,O 5a; R = Ph, solv = Me,CO 5b). The reaction of complex l a with AgCIO, (1 :1) and excess of pyridine gave the cationic complex [Pd{C(R)=C(R)C(R)=C(R)C,H,CH(Me)NH,}(py),]CIO, 6 ( R = C0,Me). The crystal structure of complex l b has been determined by X-ray diffraction. The palladium atom is bonded to Br, N, C ( l ) and to the midpoint of the C(3)-C(4) double bond in a distorted square-planar geometry.The metakarbon bond in orthopalladated tertiary amines undergoes insertion reactions with, for example, carbon monoxide, alkenes, acyl halides and alkynes, 5-7 and, upon decomposition, can afford interesting organic compounds. 5 * 8 , 9 These compounds have therefore attracted great interest in organic synthesis.Recently we have described the orthopalladation of amethylbenzylamine. ' We were interested in the reaction of these cyclometallated primary amines with alkynes, first because such reactions have not been reported yet and, secondly, because a different behaviour from their analogous complexes containing tertiary amines is expected. Thus, more stable insertion products are predicted due to their greater basic character and therefore there exists the possibility of studying the reactivity of such mono-or di-inserted complexes with different ligands to afford new types of organopalladium complexes. This is the main objective of the present work. The only reported reactions of cyclopalladated primary amines are those of CO or isocyanides with cyclopalladated benzylamine affording, after insertion and depalladation, phthalimidine or isoindolinimines, respectively. However, these results were published some time ago as a preliminary comm~nication.~

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Section: Resultsmentioning

confidence: 99%

Insertion of internal acetylenes into orthopalladated α-methylbenzylamine. Crystal structure of [Pd{C(Ph)C(Ph)C(Ph)C(Ph)C₆H₄CH(Me)NH₂}Br]

Vicente¹,

Saura‐Llamas²,

Arellano³

1995

J. Chem. Soc., Dalton Trans.

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“…The use of organopalladium complexes in organic syntheses constitutes a topic of current interest; in particular, reactions involving arylpalladium complexes and alkynes have proved to be useful for the synthesis of various types of organic compounds. − In this paper, we report a new example of this type of reaction that gives a highly functionalized spirocyclic compound. However, although reactions of isocyanides with alkyl-, − alkynyl-, − aryl-, ,− and other 23,24 organopalladium derivatives are known to give insertion products, only a few such reactions lead directly 11,12,19-21 or after reaction with other reagents 13,18 to organic products. Some heterocyclic compounds are among the more interesting of these organic products (see Scheme ). − We report in this paper a member of a new family of ketenimines that is formed by a new type of head-to-head coupling of two isocyanide molecules (see Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Palladium-Assisted Formation of Carbon−Carbon Bonds. 7.¹ Reactions of (2,3,4-Trimethoxy-6-X-phenyl)palladium Complexes with Alkynes (X = C(O)NHBu^t) and Isocyanides (X = C(O)NHBu^t, C(O)Me, CHO): Crystal and Molecular Structures of [Pd{C₆H{C(O)NHBu^t}-6-(OMe)₃-2,3,4}(bpy)](CF₃SO₃), [Pd{C(CO₂Me)C(CO₂Me)C₆H{C(O)NHBu^t}-6-(OMe)₃-2,3,4)}- Cl(PPh₃)], [Pd{C(NXy)C<

et al. 1997

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The mercuriation of 3,4,5-trimethoxy(N-tert-butylcarbamoyl)benzene with mercury(II) acetate and subsequent reaction with KCl leads to the formation of [Hg{C 6 The reaction of 2 with [PdCl 2 (MeCN) 2 ] and 2,2′-bipyridine (bpy) affords [Pd(C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4)Cl(bpy)] (3), which reacts with Tl(CF 3 SO 3 ) giving [Pd-{C 6 H{C(O)NHBu t }}(bpy)](CF 3 SO 3 ) (4). Complex 2 reacts with [PdCl 2 (MeCN) 2 ] and acetylenes RCtCR to give metallic palladium and the spirocyclic compound 10-(N-tert-butylcarbamoyl)-6,7-dimethoxy-1,2,3,4-tetraphenylspiro[4.5]-1,3,6,9-decatetraen-8-one (5) when R ) Ph or the monoinserted palladium complex [Pd{C(CO 2 Me)dC(CO 2 Me)C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4}(µ-Cl)] 2 (6) when R ) CO 2 Me. By reaction of 6 with L (1:2) or PPh 3 and Tl(CF 3 SO 3 ) (1:4:2), the complexes [Pd{C(CO 2 Me)dC(CO 2 Me)C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4}Cl(L)] (L ) PPh 3 (7), CNXy (8) (Xy ) 2,6-dimethylphenyl)) or [Pd{C(CO 2 Me)dC(CO 2 Me)C 6 H{C(O)-NHBu t }-6-(OMe) 3 -2,3,4}(PPh 3 ) 2 ](CF 3 SO 3 ) (9) are obtained respectively. The reactions of 4 and of the related complexes [Pd{C 6 H{C(O)Me}-6-(OMe) 3 -2,3,4}(bpy)](CF 3 SO 3 ) (10) or [Pd-{C 6 H{C(O)H}-6-(OMe) 3 -2,3,4}(NCMe)(bpy)](CF 3 SO 3 ) (11) with CNXy have also been studied, the following compounds being isolated: [Pd{C(dNXy)C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4}-(bpy)](CF 3 SO 3 ) (12) [Pd{C 6 H{C(O)Me}-6-(OMe) 3 -2,3,4}(CNXy)(bpy)](CF 3 SO 3 ) (13), [Pd-{C 6 H{C(O)H}-6-(OMe) 3 -2,3,4}(CNXy)(bpy)](CF 3 SO 3 ) (14), and the ketenimine 2-(2,6dimethylphenyl)-1-(((2,6-dimethylphenyl)imino)methylene)-5,6,7-trimethoxy-3-oxoisoindoline (15). The structures of 4, 7, 12, and 15 have been determined by X-ray crystallography.

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“…Although many studies on the isocyanide insertion for organopalladium aryl complexes to form palladium imidoyl compounds have been reported, the insertion of isocyanide into the palladium aryl compounds containing pseudo-halogen ligands has not been reported. 17,[24][25][26][27][28][29][30][31][32][33][34] IR spectra of imidoyl Pd(II) azido complexes 23-27 show a stretch band at 2031-2038 cm −1 due to the m(N 3 ), which is slightly shifted to lower values compared to that (2040-2051 cm −1 ) of starting materials. Interestingly, 1 H NMR spectra of each methyl group (-CH(CH 3 ) 2 ) in the 2,6-diisopropylarylimidoyl group of complexes 23-26 display four doublets coupled with the proton of the isopropyl group (-CH(CH 3 ) 2 ), which indicate the magnetically inequivalent methyl groups in solution.…”

Section: Preparation Of Cyclometallated Pd(ii) Azido Complexes Having...mentioning

confidence: 99%

Cyclometallated Pd(ii) azido complexes containing 6-phenyl-2,2′-bipyridyl or 2-phenylpyridyl derivatives: synthesis and reactivity toward organic isocyanides and isothiocyanates

et al. 2004

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Cyclometallated palladium(II) azido complexes containing C,N,N- or C,N-donor ligands, [Pd(N(3))L](HL = 6-phenyl-2,2'-bipyridine or 2-phenylpyridyl derivatives), showed different reactivities toward organic isocyanides and isothiocyanates. In particular, aryl isocyanides (CN-Ar) underwent insertion into the orthometallated Pd-C bond on the phenyl moiety of the supporting ligand (L) in [Pd(N(3))L] or [Pd(N(3))(PR(3))L] to selectively give carbodiimido [[Pd(N=C=N-Ar)L]], imidoyl [[Pd(N(3))(-C=N-Ar)(PR(3))L]], or imidoyl carbodiimido complexes [[Pd(N=C=N-Ar)(-C=N-Ar)L] or [Pd(N=C=N-Ar)(-C=N-Ar)(PR(3))L]], depending on reaction conditions. Interestingly, reactions of [Pd(N(3))(PR(3))L] with organic isothiocyanates gave unusual dinuclear complexes [(micro-SCN(4)-R)PdL](2), exhibiting the concurrent S- and N-coordinating thio-tetrazole bridge.

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The synthesis of N-heterocycles using ortho-metallated primary benzylamine complexes of palladium(II) and platinum(II)

Cited by 47 publications

References 1 publication

Insertion of internal acetylenes into orthopalladated α-methylbenzylamine. Crystal structure of [Pd{C(Ph)C(Ph)C(Ph)C(Ph)C₆H₄CH(Me)NH₂}Br]

Insertion of internal acetylenes into orthopalladated α-methylbenzylamine. Crystal structure of [Pd{C(Ph)C(Ph)C(Ph)C(Ph)C₆H₄CH(Me)NH₂}Br]

Cyclometallated Pd(ii) azido complexes containing 6-phenyl-2,2′-bipyridyl or 2-phenylpyridyl derivatives: synthesis and reactivity toward organic isocyanides and isothiocyanates

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The synthesis of N-heterocycles using ortho-metallated primary benzylamine complexes of palladium(II) and platinum(II)

Cited by 47 publications

References 1 publication

Insertion of internal acetylenes into orthopalladated α-methylbenzylamine. Crystal structure of [Pd{C(Ph)C(Ph)C(Ph)C(Ph)C6H4CH(Me)NH2}Br]

Insertion of internal acetylenes into orthopalladated α-methylbenzylamine. Crystal structure of [Pd{C(Ph)C(Ph)C(Ph)C(Ph)C6H4CH(Me)NH2}Br]

Cyclometallated Pd(ii) azido complexes containing 6-phenyl-2,2′-bipyridyl or 2-phenylpyridyl derivatives: synthesis and reactivity toward organic isocyanides and isothiocyanates

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Insertion of internal acetylenes into orthopalladated α-methylbenzylamine. Crystal structure of [Pd{C(Ph)C(Ph)C(Ph)C(Ph)C₆H₄CH(Me)NH₂}Br]

Insertion of internal acetylenes into orthopalladated α-methylbenzylamine. Crystal structure of [Pd{C(Ph)C(Ph)C(Ph)C(Ph)C₆H₄CH(Me)NH₂}Br]