Cross-coupling, palladium-catalyzed

Diederich and P. J. Stang, Metal-Catalyzed Cross-Coupling Reactions, Wiley-VCH, New York, 1998 S. P. Stanforth, Tetrahedron, 54, 263 (1998). 

Tmnsithn Metals magnesium, organozinc, and organocopper reagents. We then proceed to arylation of 

Organozinc compounds are also useful in palladium-catalyzed coupling with aryl and alkenyl halides. Procedures for arylzinc,156 alkenylzinc,157 and alkylzinc158 reagents have been developed. The ferrocenyldiphosphine dppf has been found to be an especially good Pd ligand for these reactions.159 

The 6 -phosphines dppe, dppp, and dppb were also effective for this coupling. Entry 3 is an example of use of a vinyl triflate. Entries 4 and 5 illustrate the use of perfluorobu-tanesulfonate (nonaflate) as an alternative leaving group to triflate. The organozinc 

There are a number of procedures for coupling of terminal alkynes with halides and sulfonates, a reaction that is known as the Sonogashira reaction.161 A combination of Pd(PPh3)4 and Cu(I) effects coupling of terminal alkynes with vinyl or aryl halides.162 The reaction can be carried out directly with the alkyne, using amines for deprotonation. The alkyne is presumably converted to the copper acetylide, and the halide reacts with Pd(0) by oxidative addition. Transfer of the acetylide group to Pd results in reductive elimination and formation of the observed product. 

Tetrakis(triphenylphosphine)palladium catalyzes coupling of alkenyl halides with 

A promising recent development is the extension of Pd-catalyzed cross coupling to simple enolates and enolate equivalents. This provides an important way of arylating enolates, which is normally a difficult transformation to accomplish. Use of tri-/-butylphos-phine with a catalytic amount of Pd(OAc)2 results in phenylation of the enolates of 

Arylation has also been observed with the diphosphine ligand BINAP. 

Tetrakis(triphenylphosphine)palladium catalyzes coupling of alkenyl halides with Grignard reagents and organolithium reagents. 

---

These zinc reagents are useful precursors for stereocontrolled palladium-catalyzed cross-coupling reactions, as illustrated in equations 73-80 [100, 101, 102, 103, 104, 105, 106, 107, 108] This methodology has been used to prepare new fluorinated analogues of codlemone [I09. ... 

Palladium-catalyzed cross-coupling between vinylsilane 119 and 3-iodoqui-noline 91 then assembled 92 in 83% yield. 

Heck reaction, palladium-catalyzed cross-coupling reactions between organohalides or triflates with olefins (72JOC2320), can take place inter- or intra-molecularly. It is a powerful carbon-carbon bond forming reaction for the preparation of alkenyl- and aryl-substituted alkenes in which only a catalytic amount of a palladium(O) complex is required. 

Closely related to the Heck reaction is the Sonogashira reaction i.e. the palladium-catalyzed cross-coupling of a vinyl or aryl halide 20 and a terminal alkyne 21 ... 

Palladium-catalyzed cross-coupling with organoboron compounds... 

The late Professor J. K. Stille pioneered the development of a very effective and versatile palladium-mediated C-C bond forming method - the palladium-catalyzed cross-coupling of organic electrophiles with organostannanes.48 This process continues to enjoy much success in organic synthesis because it proceeds in high yields under mild reaction conditions and because it tolerates a... 

The key step in a short and efficient synthesis of pleraplysillin-1 (127) is the palladium-catalyzed cross-coupling of vinylstannane 125 with vinyl triflate 126 (see Scheme 33). This synthesis is noteworthy in two respects. First, vinyl triflate 126 is generated regio-specifically from the kinetic enolate arising from a conjugate reduction of enone 124 the conjugate reduction of an enone is, in fact, a... 

Z)-3-(Tributylstannyl)allylamine participates in a palladium-catalyzed cross-coupling reaction with 2-bromobenzaldehyde (73, R = H) to give 3//-2-benzazepine (75, R = H). A similar reaction with the corresponding acetophenone 73 (R = Me) produces 1 -methyl-3//-2-benzazepine (75 R = Me), whereas with ethyl 2-bromobenzoate (73, R = OMe), 3//-2-benzazepin-(12/7)-one (74) is formed.237... 

The Suzuki reaction was also used to prepare the polyketone since this particular reaction tolerates the subsequent step (Scheme 6.19).135 Palladium-catalyzed cross-coupling of aromatic diacid chlorides and bis(trimethylstannane) monomers was utilized to prepare poly(arylene ether ketone)s.136... 

PALLADIUM CATALYZED CROSS-COUPLING OF (Z)-l-HEPTENYLDIMETHYLSILANOL WITH 4-IODOANISOLE (Z)-l-HEPTENYL)-4-METHOXYBENZENE... 

The palladium-catalyzed cross-coupling of alkenylsilanols has been extensively studied with respect to the structure of both the silicon component and the acceptor halide. The preferred catalyst for coupling of aryl iodides is Pd(dba)2 and for aryl bromides it is [allylPdCl]2. The most effective promoter is tetrabutylammonium fluoride used as a 1.0M solution in THF. In general the coupling reactions occur under mild conditions (room temperature, in 10 min to 12 hr) and some are even exothermic. 

PLATINUM CATALYZED HYDROSILYLATION AND PALLADIUM CATALYZED CROSS-COUPLING ONE-POT HYDROARYLATION OF 1-HEPTYNE TO (E)-l-(l-HEPTENYL)-4-... 

SYNTHESIS OF N-( -BUTOXYCARBONYL)-P-IODOALANINE METHYL ESTER A USEFUL BUILDING BLOCK IN THE SYNTHESIS OF NONNATURAL a-AMINO ACIDS VIA PALLADIUM CATALYZED CROSS COUPLING REACTIONS... 

Palladium catalyzed cross-coupling reactions of arylhalides or halide equivalents with various nucleophiles have been shown to be highly effective and practical... 

King AO, Yasuda N (2004) Palladium-Catalyzed Cross-Coupling Reactions in the Synthesis of Pharmaceuticals. 6 205-246 King NP, see Nicolaou KC, He Y (1998) 1 73-104... 

Over the last decade, the chemistry of the carbon-carbon triple bond has experienced a vigorous resurgence [1]. Whereas construction of alkyne-con-taining systems had previously been a laborious process, the advent of new synthetic methodology based on organotransition metal complexes has revolutionized the field [2]. Specifically, palladium-catalyzed cross-coupling reactions between alkyne sp-carbon atoms and sp -carbon atoms of arenes and alkenes have allowed for rapid assembly of relatively complex structures [3]. In particular, the preparation of alkyne-rich macrocycles, the subject of this report, has benefited enormously from these recent advances. For the purpose of this review, we Emit the discussion to cychc systems which contain benzene and acetylene moieties only, henceforth referred to as phenylacetylene and phenyldiacetylene macrocycles (PAMs and PDMs, respectively). Not only have a wide... 

Negishi E, Tan Z (2005) Diastereoselective, Enantioselective, and Regioselective Carbo-alumination Reactions Catalyzed by Zirconocene Derivatives. 8 139-176 Netherton M, Fu GC (2005)Palladium-catalyzed Cross-Coupling Reactions of Unactivated Alkyl Electrophiles with Organometallic Compounds. 14 85-108 NicolaouKC, KingNP, He Y (1998) Ring-Closing Metathesis in the Synthesis of EpothUones and Polyether Natural Products. 1 73-104 Nishiyama H (2004) Cyclopropanation with Ruthenium Catalysts. 11 81-92 Noels A, Demonceau A, Delaude L (2004) Ruthenium Promoted Catalysed Radical Processes toward Fine Chemistry. 11 155-171... 

Scheme 8.10. Palladium-Catalyzed Cross Coupling of Organometallic Reagents with...

Table 1 Air-stable palladium-catalyzed cross-coupling reactions.

---