A halide displacement

In the reaction of CbSi" with acid chlorides, two trichlorosilyl groups are introduced (equation 14) this probably proceeds via a two-step mechanism. The first step involves reductive silylation and loss of the carbonyl group the second involves a halide displacement as above. These trichlorosilyl compounds may be further treated with Grignard... 

The osmium complex OsCl(CO)(NO)(PPh3)2 can be converted into the corresponding cationic ethylene complex by a halide displacement promoted by Ag(I) ... 

Scheme 9 Access to amine-stabilized dimethylaluminum cations via a halide displacement reaction...

Next an alkyl halide (the alkylating agent) is added to the solution of sodium acetylide Acetylide ion acts as a nucleophile displacing halide from carbon and forming a new carbon-carbon bond Substitution occurs by an 8 2 mechanism... 

The Williamson ether synthesis (Sec tion 16 6) An alkoxide ion displaces a halide or similar leaving group in an Sn2 reaction The alkyl halide cannot be one that is prone to elimination and so this reaction is limited to methyl and primary alkyl halides There is no limitation on the alkoxide ion that can be used... 

Halide Displacement. Hahde displacement is a method used to prepare thiols that are not readily available by normal means. It requires a two-phase, water—organic system, that can be quite corrosive. Normally, this type of reaction, a classic Sj 2 type, is undertaken in HasteUoy or glass-lined... 

Historically, simple Vz-alkyl ethers formed from a phenol and a halide or sulfate were cleaved under rather drastic conditions (e.g., refluxing HBr). New ether protective groups have been developed that are removed under much milder conditions (e.g., via nucleophilic displacement, hydrogenolysis of benzyl ethers, and mild acid hydrolysis of acetal-type ethers) that seldom affect other functional groups in a molecule. 

In the first century of "organic" chemistry much attention was given to the structures of carbogens and their transformations. Reactions were classified according to the types of substrates that underwent the chemical change (for example "aromatic substitution," "carbonyl addition," "halide displacement," "ester condensation"). Chemistry was taught and learned as transformations characteristic of a structural class (e.g. phenol, aldehyde) or structural subunit... 

Only one of these methods, namely the reaction of halides with lithium aluminum deuteride, is a true displacement reaction, following the same course as the previously discussed displacement of sulfonate esters (section Vl-A). Thus, lithium aluminum deuteride treatment of 7a- and 7jS-bromo-3 -benzoyloxy-5a-cholestanes (195) and (196) gives the corresponding deuterium labeled cholestanols (197) and (198) respectively." ... 

The postulated steps that constitute the Suzuki coupling process are shown in Scheme 25. After oxidative addition of the organic halide to the palladium(o) catalyst, it is presumed that a metathetical displacement of the halide substituent in the palladium(ii) complex A by ethoxide ion (or hydroxide ion) takes place to give an alkoxo-palladium(ff) complex B. The latter complex then reacts with the alkenylborane, generating the diorganopalladium complex C. Finally, reductive elimination of C furnishes the cross-coupling product (D) and regenerates the palladium(o) catalyst. 

Mercurydl) halides displace Me3Sn groups from a transition-metal carbonyl derivative ... 

Probably the most common aromatic nucleophilic displacement reactions involve the displacement of Hal from a halide activated by electron-withdrawing groups, e.g. (80) ... 

The group ofWalborsky probably has described one of the first true anionic/radi-cal domino process in their synthesis of the spirocyclopropyl ether 2-733 starting from the tertiary allylic bromide 2-730 (Scheme 2.161) [369]. The first step is a Michael addition with methoxide which led to the malonate anion 2-731. It follows a displacement of the tertiary bromide and a subsequent ring closure which is thought to involve a SET from the anionic center to the carbon-bromine anti bonding orbital to produce the diradical 2-732 and a bromide anion. An obvious alternative Sn2 halide displacement was excluded due to steric reasons and the ease with which the reaction proceeded. 

Construction of isolated or benzannulated five-membered rings of NHPs can be accomplished by means of various condensation or cycloaddition reactions all of which involve interaction of an electrophilic Pj and a nucleophilic C2N2 building block. Salts containing 1,3,2-diazaphospholide anions or 1,3,2-diazaphospholenium cations can be directly accessed by some of these reactions but the products are in most cases neutral 1,3,2-diazaphospholes or NHP. A particularly concerted effort has been directed toward the synthesis of P-halogen-substituted NHP which are capable of undergoing further reactions via halide displacement or halide abstraction and serve thus as entry points for the preparation of a wide variety of neutral and cationic NHP derivatives. 1,3,2-Diazaphospholide anions are normally accessed by deprotonation of suitable iV-H-substituted precursors. 

Representative cyclizations. Typically, a given cyclization involves nucleophilic displacement of a halide or tosylate by alkoxide or phenoxide ion (that is, a Williamson synthesis) even though such reactions are frequently quite slow. Schemes [4.1], [4.2] and [4.3] give representative... 

Organometallic compounds or carbanions undergo a number of reactions in which the carbanion or carbanion-like moiety of the organometallic compound acts as a nucleophilic displacing agent. Examples are the formation of hydrocarbons from alkyl halides, alkyl halides from halogens, and ketones from acid chlorides or esters. The latter two reactions are closely related to the base-catalyzed condensations and are perhaps additions as well as displacement reactions. Related addition reactions are the carbonation of organometallic compounds and the addition to ketones or aldehydes. 

R = Pr) via a bromide displacement process. Halide displacements have been observed previously in the reactions of carbenes with Me3SiI (38). However, this represents the first such reaction with a haloborane. The X-ray crystal structure of 49 was determined and showed that both heterocyclic rings are planar and that the interpla-nar angle is 92.9°. The B-C(carbene) bond distance of 1.580(11) A is comparable to that found in 32 (1.603(3) A). 

Aguilar, A.M. and Daigle, D., Vinyl halide displacement by metallo organo-phosphides. Preparation of fra s-(f-styryldiphenylphosphine oxide and sulfide, /. Org. Chem., 30, 2826, 1965. 

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