0000000000156898
AUTHOR
Konstantin V. Luzyanin
PdII-mediated integration of isocyanides and azide ions might proceed via formal 1,3-dipolar cycloaddition between RNC ligands and uncomplexed azide
Reaction between equimolar amounts of trans-[PdCl(PPh3)2(CNR)][BF4] (R = t-Bu 1, Xyl 2) and diisopropylammonium azide 3 gives the tetrazolate trans-[PdCl(PPh3)2(N4t-Bu)] (67%, 4) or trans-[PdCl(PPh3)2(N4Xyl)] (72%, 5) complexes. 4 and 5 were characterized by elemental analyses (C, H, N), HRESI+-MS, 1H and 13C{1H} NMR spectroscopies. In addition, the structure of 4 was elucidated by a single-crystal X-ray diffraction. DFT calculations showed that the mechanism for the formal cycloaddition (CA) of N3− to trans-[PdCl(PH3)2(CNMe)]+ is stepwise. The process is both kinetically and thermodynamically favorable and occurs via the formation of an acyclic NNNCN-intermediate. The second step of the fo…
ADC-Based Palladium Catalysts for Aqueous Suzuki Miyaura Cross-Coupling Exhibit Greater Activity than the Most Advantageous Catalytic Systems
The reaction between the equimolar amounts of cis-[PdCl2(CNR1)2] (R1 = cyclohexyl (Cy) (1), tBu (2)) and the carbohydrazides R2CONHNH2 (R2 = Ph (5), 4-ClC6H4 (6), 3-NO2C6H4 (7), 4-NO2C6H4 (8), 4-CH3C6H4 (9), 3,4-(MeO)2C6H3 (10), naphth-1-yl (11), fur-2-yl (12), 4-NO2C6H4CH2 (13), Cy (14), 1-(4-fluorophenyl)-5-oxopyrrolidin-3-yl (15), (pyrrolidin-1-yl)C(O) (16)) proceeds in refluxing CHCl3 for ca. 4 h. A subsequent workup provided the aminocarbene species cis-[PdCl2{C(NHNHC(O)R2)═N(H)R1}(CNR1)] (18–33) in good to excellent (80–95%) isolated yields. The coupling of equimolar amounts of cis-[PdCl2(CNR1)2] (R1 = Cy (1), tBu (2), 2,6-Me2C6H3 (Xyl) (3), 2-Cl-6-MeC6H3 (4)) and PhSO2NHNH2 (17) occu…
Palladium-ADC complexes as efficient catalysts in copper-free and room temperature Sonogashira coupling
Abstract The metal-mediated coupling between cis-[PdCl2(CNR1)2] [R1 = cyclohexyl (Cy) 1, t-Bu 2, 2,6-Me2C6H3 (Xyl) 3, 2-Cl-6-MeC6H3 4] and hydrazones H2NN CR2R3 [R2, R3 = Ph 5; R2, R3 = C6H4(OMe-4) 6; R2/R3 = 9-fluorenyl 7; R2 = H, R3 = C6H4(OH-2) 8] provided carbene complexes cis-[PdCl2{C(N(H)N CR2R3) N(H)R1}(CNR1)] (9–24) in good (80–85%) yields. Complexes 9–24 showed high activity [yields up to 99%, and turnover numbers (TONs) up to 3.7 × 104] in the Sonogashira coupling of various aryl iodides with a range of substituted aromatic alkynes without the need of copper co-catalyst. The catalytic procedure runs at 80 °C for 1 h in EtOH using K2CO3 as a base. No formation of homocoupling or ac…
Application of palladium complexes bearing acyclic amino(hydrazido)carbene ligands as catalysts for copper-free Sonogashira cross-coupling
Abstract Metal-mediated coupling of one isocyanide in cis-[PdCl2(CNR1)2] (R1 = C6H11 (Cy) 1, tBu 2, 2,6-Me2C6H3 (Xyl) 3, 2-Cl-6-MeC6H3 4) and various carbohydrazides R2CONHNH2 [R2 = Ph 5, 4-ClC6H4 6, 3-NO2C6H4 7, 4-NO2C6H4 8, 4-CH3C6H4 9, 3,4-(MeO)2C6H3 10, naphth-1-yl 11, fur-2-yl 12, 4-NO2C6H4CH2 13, Cy 14, 1-(4-fluorophenyl)-5-oxopyrrolidine-3-yl 15, (pyrrolidin-1-yl)C(O) 16, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propane-1-yl 17, EtNHC(O) 18] or sulfohydrazides R3SO2NHNH2 [R3 = Ph 19, 4-MeC6H4 20] led to a series of (hydrazido)(amino)carbene complexes cis-[PdCl2{ C (NHNHX) N(H)R1}(CNR1)]; X = COR2, SO2R3 (21–48, isolated yields 60–96%). All prepared species were characterized by elemental…
Palladium(II)-Mediated Addition of Benzenediamines to Isocyanides: Generation of Three Types of Diaminocarbene Ligands Depending on the Isomeric Structure of the Nucleophile
Coupling of the palladium-bis(isocyanide) complexes cis-[PdCl2(CNR)2] (R = 2,6-Me2C6H3 1, 2-Cl-6-MeC6H3 2) with benzene-1,3-diamine (BDA1) leads to the diaminocarbene species cis-[PdCl2(CNR){C(NHR)═NH(1,3-C6H4NH2)}] (5 and 6, respectively). In this reaction, BDA1 behaves as a monofunctional nucleophile that adds to one of the RNC ligands by one amino group. By contrast, the reaction of 1 and 2 with benzene-1,4-diamine (BDA2) involves both amino functionalities of the diamine and leads to the binuclear species [cis-PdCl2(CNR){μ-C(NHR)═NH(1,4-C6H4)NH═C(NHR)}-(cis)-PdCl2(CNR)] (6 and 7) featuring two 1,4-bifunctional diaminocarbene ligands. The reaction of cis-[PdCl2(CNR)2] (R = cyclohexyl 3) …
CCDC 912875: Experimental Crystal Structure Determination
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CCDC 1501943: Experimental Crystal Structure Determination
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CCDC 1501944: Experimental Crystal Structure Determination
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CCDC 1435501: Experimental Crystal Structure Determination
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CCDC 1435504: Experimental Crystal Structure Determination
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CCDC 1435506: Experimental Crystal Structure Determination
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CCDC 912877: Experimental Crystal Structure Determination
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CCDC 912876: Experimental Crystal Structure Determination
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CCDC 1414621: Experimental Crystal Structure Determination
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CCDC 1501945: Experimental Crystal Structure Determination
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CCDC 1435503: Experimental Crystal Structure Determination
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CCDC 1435502: Experimental Crystal Structure Determination
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CCDC 1435505: Experimental Crystal Structure Determination
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