- Long-Lived, Strongly Emissive, and Highly Reducing Excited States in Mo(0) Complexes with Chelating Isocyanides
-
Newly discovered tris(diisocyanide)molybdenum(0) complexes are Earth-abundant isoelectronic analogues of the well-known class of [Ru(α-diimine)3]2+ compounds with long-lived 3MLCT (metal-to-ligand charge transfer) excited
- Herr, Patrick,Glaser, Felix,Büldt, Laura A.,Larsen, Christopher B.,Wenger, Oliver S.
-
supporting information
p. 14394 - 14402
(2019/10/11)
-
- Selective ortho C?H Cyanoalkylation of (Diacetoxyiodo)arenes through [3,3]-Sigmatropic Rearrangement
-
We herein report a robust catalyst-free cross-coupling between ArI(OAc)2 and α-stannyl nitriles, aided by TMSOTf. The transformation introduces a cyanoalkyl group to the ortho position of ArI(OAc)2 and simultaneously reduces the aryl iodine(III) to iodide, thus providing α-(2-iodoaryl) nitrile as the product. This transformation could be completed within 5 min at ?78 °C and features superb functional-group tolerance and efficient scalability. DFT calculations indicate that the formation of a ketenimine(aryl)iodonium intermediate and subsequent [3,3]-sigmatropic rearrangement are involved as key steps.
- Tian, Junsong,Luo, Fan,Zhang, Chaoshen,Huang, Xin,Zhang, Yage,Zhang, Lei,Kong, Lichun,Hu, Xiaochun,Wang, Zhi-Xiang,Peng, Bo
-
supporting information
p. 9078 - 9082
(2018/07/25)
-
- Palladium-Catalyzed, ortho-Selective C-H Halogenation of Benzyl Nitriles, Aryl Weinreb Amides, and Anilides
-
A palladium-catalyzed, ortho-selective C-H halogenation methodology is reported herein. The highlight of the work is the highly selective C(sp2)-H functionalization of benzyl nitriles in the presence of activated C(sp3)-H bond, which results in good yields of the halogenated products with excellent regioselectivity. Along with benzyl nitriles, aryl Weinreb amides and anilides have been evaluated for the transformation using aprotic conditions. Mechanistic studies yield interesting aspects with respect to the pathway of the reaction and the directing group abilities.
- Das, Riki,Kapur, Manmohan
-
p. 1114 - 1126
(2018/06/18)
-
- Approach to the synthesis of indoline derivatives from diaryliodonium salts
-
An effective method of constructing the indoline moiety via intramolecular nucleophilic ring closure of a diaryliodonium salt is described. Diacetoxyiodoarene compounds (1a-1e) were converted into intermediate Koser's reagent and coupled with arylstannanes (7-10) to form diaryliodonium salts (11a-14e). Indoline compounds with different N-protecting groups, 15, 16, 17, and 18, were synthesized in higher yields by treating salts (11a-14e) with Cs2CO3 and TEMPO. Regardless of the electronic environment of five para-substituted iodoarenes and the natures of four N-protected arylstannane groups, the conversion proceeded well to afford corresponding indolines in yields of 72-84 and 70-84%, respectively.
- Landge, Kamalkishor P.,Jang, Keun Sam,Lee, Sang Yeul,Chi, Dae Yoon
-
experimental part
p. 5705 - 5713
(2012/09/07)
-
- Mo(CO)6-mediated carbamoylation of aryl halides
-
A simple method for the synthesis of amides has been developed by molybdenum-mediated carbamoylation of aryl halides. Whereas the conventional palladium-catalyzed three-component coupling reaction requires a large excess of gaseous carbon monoxide, the incorporation of carbon monoxide in this Mo-mediated carbamoylation reaction is so efficient that it requires only a slight excess amount of carbon monoxide in the form of its molybdenum complex, Mo(CO)6. The reaction is applicable for the synthesis of a wide variety of not only secondary and tertiary amides but also primary amides by using aqueous ammonia.
- Ren, Wei,Yamane, Motoki
-
supporting information; scheme or table
p. 8410 - 8415
(2011/02/23)
-
- A mild inter- and intramolecular amination of aryl halides with a combination of CuI and CsOAc
-
A unique combination of CuI and CsOAc was found to catalyze aryl amination under mild conditions. The reaction takes place at room temperature or at 90 °C with broad functional group compatibility. The intramolecular reaction was able to form five-, six-, and seven-membered rings with various protecting groups on the nitrogen atom. The scope of the intermolecular amination, as well as its applications to unsymmetrical N,N′-dialkylated phenylenediamines, was investigated.
- Kubo, Tetsuji,Katoh, Chiharu,Yamada, Ken,Okano, Kentaro,Tokuyama, Hidetoshi,Fukuyama, Tohru
-
supporting information; experimental part
p. 11230 - 11236
(2009/04/11)
-
- Facile one-pot synthesis of 2-aryl-substituted nitriles and 2-aryl-3-keto nitriles via benzyne reaction
-
2-Aryl-substituted nitriles were prepared in good to excellent yields in a one-pot reaction by the reaction of benzyne, generated using neutral conditions from (phenyl)[o-(trimethylsilyl)-phenyl]iodonium triflate, and 2-lithionitriles. 3-Keto nitriles substituted at the 2-position were obtained in good yields when these reactions were trapped with acid chlorides. The mechanism of the benzyne reaction in terms of a N-lithiobenzocyclobutanimine intermediate is discussed. Copyright Taylor & Francis Group, LLC.
- Kamila, Sukanta,Koh, Benjamin,Biehl, Edward R.
-
p. 3493 - 3507
(2007/10/03)
-
- A new synthesis of phenolic 1-hydroxy-1-phenyl-2,3,4,5-tetrahydro-1H-3-Benzazepines
-
7,8-Dihydroxy-1-phenyl- and 1-(3- and 4-hydroxyphenyl)-1-hydroxy-2,3,4,5-tetrahydro-1H-3-benzazepine derivatives (2a,b) and (3a-c) were synthesized by intramolecular Barbier reaction of N-(2-iodophenethyl)-phenacylamines (5a,b) and (12a-c) with n-C4
- Ikeuchi, Motoki,Ikeuchi, Miyuki,Inoue, Kumiko,Yamamoto, Syuhei,Yamauchi, Aiko,Kihara, Masaru
-
p. 2925 - 2935
(2007/10/03)
-
- Copper(I) mediated intramolecular cyclization of 2-(2-amino-phenylethynyl)benzoic and [2-(2-aminophenylethynyl)phenyl]acetic acid esters: A new synthetic step towards isoindolo[2,1-a]indoles and 5H-indolo[2,1-a]isoquinolines
-
We describe herein parallel synthetic routes to isoindolo[2,1-a]indoles and 5H-indolo[2,1-a]isoquinolines from 2-(2-aminophenylethynyl)benzoic acid esters and [2-(2-aminophenylethynyl)phenyl]acetic acid esters, respectively.
- Reboredo, Francisco J.,Treus, Mónica,Estévez, Juan C.,Castedo, Luis,Estévez, Ramón J.
-
p. 1603 - 1606
(2007/10/03)
-
- Regioselective synthesis of isoquino[1,2-b][3]benzazepines (homoprotoberberines) through 11-membered-ring stilbene lactams obtained by radical macrocyclization
-
Silylated 11-membered-ring stilbene lactams 3 (E and Z) were easily prepared by intramolecular addition of an aryl radical to a trimethylsilylacetylene. Oxidation of their hindered stilbene double bonds with dioxiranes gave oxidative cleavage of their electron-rich aromatic rings. However, reduction of the amide to an amine functionality in both lactams (E and Z) triggers a regioselective [7,6]-transannular cyclization to isoquino[1,2-b][3]benzazepines (homoprotoberberines).
- Rodriguez, Gema,Castedo, Luis,Dominguez, Domingo,Saa, Carlos,Adam, Waldemar
-
p. 4830 - 4833
(2007/10/03)
-
- Synthesis of medium-ring nitrogen heterocycles via palladium-catalyzed heteroannulation of 1, 2-dienes
-
Seven-, eight-, and nine-membered-ring nitrogen heterocycles are readily prepared by the palladiumcatalyzed heteroannulation of a variety of 1, 2-dienes by a range of tosylamide- and amine-containing aryl and vinylic halides. The ease of ring formation is
- Larock, Richard C.,Tu, Chi,Pace, Paola
-
p. 6859 - 6866
(2007/10/03)
-
- Tandem radical reactions of isonitriles with 2-pyridonyl and other aryl radicals: Scope and limitations, and a first generation synthesis of (±)-camptothecin
-
Photolysis of N-propargyl-6-halo-2-pyridones and related aromatic halides in the presence of aryl isonitriles provides tetra- and penta-cyclic products in a single step by a sequence of radical addition to the isonitrile followed by two cyclizations. The scope and limitations of the process are described along with a first generation synthesis of racemic camptothecin.
- Curran, Dennis P.,Liu, Hui,Josien, Hubert,Ko, Sung-Bo
-
p. 11385 - 11404
(2007/10/03)
-
- Palladium-catalyzed carbonylative cyclization via trapping of acylpalladium derivatives with internal enolates. Its scope and factors affecting the C-to-O ratio
-
The Pd-catalyzed carbonylative cyclization reaction involving ω-acyl-substituted acylpalladium derivatives can proceed via intramolecular trapping with either C- or O-enolates; the preferential formation of either 5- or 6-membered rings dictates the C-to-
- Negishi, El-Ichi,Coperet, Christophe,Sugihara, Takumichi,Shimoyama, Izumi,Zhang, Yantao,Wu, Guangzhong,Tour, James M.
-
p. 425 - 436
(2007/10/02)
-
- Antihypertensive Activity of 6-Arylpyridopyrimidin-7-amine Derivatives
-
A series of 51 6-arylpyridopyrimidin-7-amine derivatives was prepared and evaluated for antihypertensive activity in the conscious spontaneously hypertensive rat.A number of these compounds, notably 6-(2,6-dichlorophenyl)-2-methylpyridopyrimidin-7-amine (36), lowered blood pressure in these rats in a gradual and sustained manner to normotensive levels at oral doses of 10-50 mg/kg.Normalized blood pressure levels could then be maintained by single daily oral doses.The effect of structural variation in the 6-aryl group and in the 2 and 4 positions of the pyridopyrimidine ring on activity is reported and discussed.
- Bennett, Lawrence R.,Blankley, C. John,Fleming, Robert W.,Smith, Ronald D.,Tessman, Deirdre K.
-
p. 382 - 389
(2007/10/02)
-
