3.7. Palladium Nanoparticles as Catalysts 888 3.8. Other Transition-Metal Complexes 888 3.9. Transition-Metal-Free Reactions 889 4. Applications 889 4.1. Alkynylation of Arenes 889 4.2. Alkynylation of Heterocycles 891 4.3. Synthesis of Enynes and Enediynes 894 4.4. Synthesis of Ynones 896 4.5. Synthesis of Carbocyclic Systems 897 4.6. Synthesis of Heterocyclic Systems 898 4.7. Synthesis of Natural Products 903 4.8. Synthesis of Electronic and Electrooptical Molecules 906

https://www.chem.ccu.edu.tw/~joyce/referance/ericyang/Chem.%20Rev/Chem.%20Rev.%202007,%20107,%20874-922.pdf

The Sonogashira Reaction: A Booming Methodology in Synthetic Organic Chemistry†

ion. The oxidative addition mechanism was originally proposed22i because of the lack of a strong rate dependence on polar factors and on the acidity of the medium. Later, however, the electrophilic substitution mechanism also was proposed. Recently, the oxidative addition mechanism was confirmed by investigations into the decomposition and protonolysis of alkylplatinum complexes, which are the reverse of alkane activation. There are two routes which operate in the decomposition of the dimethylplatinum(IV) complex Cs2Pt(CH3)2Cl4. The first route leads to chloride-induced reductive elimination and produces methyl chloride and methane. The second route leads to the formation of ethane. There is strong kinetic evidence that the ethane is produced by the decomposition of an ethylhydridoplatinum(IV) complex formed from the initial dimethylplatinum(IV) complex. In D2O-DCl, the ethane which is formed contains several D atoms and has practically the same multiple exchange parameter and distribution as does an ethane which has undergone platinum(II)-catalyzed H-D exchange with D2O. Moreover, ethyl chloride is formed competitively with H-D exchange in the presence of platinum(IV). From the principle of microscopic reversibility it follows that the same ethylhydridoplatinum(IV) complex is the intermediate in the reaction of ethane with platinum(II). Important results were obtained by Labinger and Bercaw62c in the investigation of the protonolysis mechanism of several alkylplatinum(II) complexes at low temperatures. These reactions are important because they could model the microscopic reverse of C-H activation by platinum(II) complexes. Alkylhydridoplatinum(IV) complexes were observed as intermediates in certain cases, such as when the complex (tmeda)Pt(CH2Ph)Cl or (tmeda)PtMe2 (tmeda ) N,N,N′,N′-tetramethylenediamine) was treated with HCl in CD2Cl2 or CD3OD, respectively. In some cases H-D exchange took place between the methyl groups on platinum and the, CD3OD prior to methane loss. On the basis of the kinetic results, a common mechanism was proposed to operate in all the reactions: (1) protonation of Pt(II) to generate an alkylhydridoplatinum(IV) intermediate, (2) dissociation of solvent or chloride to generate a cationic, fivecoordinate platinum(IV) species, (3) reductive C-H bond formation, producing a platinum(II) alkane σ-complex, and (4) loss of the alkane either through an associative or dissociative substitution pathway. These results implicate the presence of both alkane σ-complexes and alkylhydridoplatinum(IV) complexes as intermediates in the Pt(II)-induced C-H activation reactions. Thus, the first step in the alkane activation reaction is formation of a σ-complex with the alkane, which then undergoes oxidative addition to produce an alkylhydrido complex. Reversible interconversion of these intermediates, together with reversible deprotonation of the alkylhydridoplatinum(IV) complexes, leads to multiple H-D exchange

Activation of c-h bonds by metal complexes

Collectively, palladium-catalyzed coupling reactions represent some of the most powerful and versatile tools available to synthetic organic chemists. Their widespread popularity stems in part from the fact that they are generally tolerant to a large number of functional groups, which allows them to be employed in a wide range of applications. However, for many years a major limitation of palladium-catalyzed coupling processes has been the poor reactivity of aryl chlorides, which from the standpoints of cost and availability are more attractive substrates than the corresponding bromides, iodides, and triflates. Traditional palladium/triarylphosphane catalysts are only effective for the coupling of certain activated aryl chlorides (for example, heteroaryl chlorides and substrates that bear electron-withdrawing groups), but not for aryl chlorides in general. Since 1998, major advances have been described by a number of research groups addressing this challenge; catalysts based on bulky, electron-rich phosphanes and carbenes have proved to be particularly mild and versatile. This review summarizes both the seminal early work and the exciting recent developments in the area of palladium-catalyzed couplings of aryl chlorides.

/pdf/palladium-catalyzed-coupling-reactions-of-aryl-chlorides-2jld2ekpnf.pdf

Palladium-Catalyzed Coupling Reactions of Aryl Chlorides

6.4. Polyynes 3123 6.5. Using R-Hydroxy Stannanes 3124 6.6. Using the Hurtley Reaction 3124 6.7. Using a Methylenation Reaction 3125 7. Conclusions and Future Prospects 3125 8. Uncommon Abbreviations 3125 9. Acknowledgments 3125 10. Note Added in Proof 3125 11. References 3126 * Authorstowhomcorrespondenceshouldbeaddressed(evano@chimie.uvsq.fr, nicolas.blanchard@uha.fr). † Université de Versailles Saint Quentin en Yvelines. ‡ Université de Haute-Alsace. Chem. Rev. 2008, 108, 3054–3131 3054

Copper-mediated coupling reactions and their applications in natural products and designed biomolecules synthesis.

https://www.chem.ccu.edu.tw/~joyce/referance/ericyang/Coord.%20Chem.%20Rev/Coord.%20Chem.%20Rev.%202004,%20248,%202337-2364.pdf

Copper in cross-coupling reactions: The post-Ullmann chemistry

A Convenient Synthesis of Primary 2-Hydroxyorganophosphines from Red Phosphorus and Oxiranes

The present investigation deals with interrelations between thioethers of the types R1CH2CR2 = CH -C≡CSCH3 (3-en-1-yne thioethers)



R1CH = C(R2)CHC = CHSCH3 (1,2,4-trienyl thioethers)



R1CHC(R2)C≡CCH2SCH3 (4-en-2-yne thioethers) and



R1CH2CR2 = C = C=CHSCH3 (1,2,3-trienyl thioethers). Under the influence of sodium ethoxide in liquid ammonia all compounds with R1=H are isomerised quantitatively into 3-en-1-yne thioethers CH3 − C(R2)=CH-C ≡ CSCH3, whereas the homologues with R1 = CH3 are quantitatively converted into a mixture of 1,2,4-trienyl thioether and 4-en-2-yne thioether. For further details see Table I.



Treatment of our substrates with an excess of sodamide in liquid ammonia and subsequent hydrolysis always produces 1,2,4-trienyl thioethers; 1,2,3-trienyl thioethers are the presumed intermediates (Tables II-V).



The yields of the sodamide reactions are often rather low because of side-reactions, among which polymerisation is included. Certain substrates suffer extensive loss of the thioether group by nucleophilic attack at sulfur (see Table II).



In Appendix III a simple method for expressing the notation of unsaturated systems is developed; it is useful in drawing conveniently arranged diagrams depicting interrelations.

Interrelation of thioethers containing conjugated systems with 6π‐electrons: (Base‐catalysed isomerisations in liquid ammonia)

The reaction of 1,3-dilithio-3-phenylpropyne with methyl isothiocyanate in THF-hexane at -90 to -55°C, followed by successive treatment of intermediate product with a donor of protons, superbase, and alkyl halide, yields isomeric iminocyclobutenes and iminothietanes in addition to the expected aminothiophene. The ratio of the products depends on the amount and nature of proton donor (MeOH, t-BuOH), base (MeONa, t-BuOM, M = Li, Na, K; t-AmOK), co-solvent (DMSO, HMPA), and alkyl halide (MeI, EtI, BuBr). The system t-BuOH(MeOH)-t-BuOK-DMSO is the most favorable for the formation of the corresponding iminocyclobutene.

New Approach to the Synthesis of Strained Cyclic Systems: I. Iminocyclobutenes and Iminothietanes from 1,3-Dilithio-3-phenylpropyne and Methyl Isothiocyanate

A new type of base-catalysed isomerisation of conjugated enynes leads to the reversed enyne systems. The preparative conversion of 1-(dialkylamino)-3-buten-1-ynes (1) into 1-(dialkylamino)-1-buten-3-ynes (2) is presented.

A new type of base‐induced isomerisation of 1,3‐enynes; the reversal of an enyne system

A new method of the selective generation of mono- or diphosphide anions from red phosphorus by the system Li/NH3 liq in the presence of t-BuOH has been developed.

Lambert Brandsma

Papers

A Convenient Synthesis of Primary 2-Hydroxyorganophosphines from Red Phosphorus and Oxiranes

Interrelation of thioethers containing conjugated systems with 6π‐electrons: (Base‐catalysed isomerisations in liquid ammonia)

New Approach to the Synthesis of Strained Cyclic Systems: I. Iminocyclobutenes and Iminothietanes from 1,3-Dilithio-3-phenylpropyne and Methyl Isothiocyanate

A new type of base‐induced isomerisation of 1,3‐enynes; the reversal of an enyne system

t-Butyl Alcohol-Assisted Fission of the P-P Bonds in Red Phosphorus with Lithium in Liquid Ammonia