Alkenyl chlorides alkylation

Simple alkyl and alkenyl ethers of pentaerythritol are produced on direct reaction of the polyol and the requited alkyl or alkenyl chloride in the presence of quaternary alkylamine bromide (44). AHyl chloride produces the pentaerythritol tetraHyl ether [1471 -18-7],... 

Symmetrical 2,2-disubstituted-l-lithio-l-chloroalkenes mono-insert cleanly into zirconacycles to give trisubstituted olefin products in high yield following protic work-up of the ring-expanded six-membered zirconacycle (Scheme 3.18 R1 = R2 = alkyl) [48]. The insertion of non-symmetrical 2,2-disubstituted alkenyl carbenoids has not yet been reported. A wide range of 2-monosubstituted alkenyl carbenoids (51, 52, 60, 62) arising from in situ deprotonation of alkenyl chlorides can be successfully inserted into zirconacyclopen-tanes and -pentenes with the expected inversion of configuration at the carbenoid carbon [49,50],... 

SCHEME 67. Alkylation of alkenyl chlorides with alkylmagnesiums in the presence of Pd catalysts... 

SCHEME 68. Pd- or Ni-catalyzed alkylation of aryl and alkenyl chlorides with alkylzincs... 

Alkenyl- -chlorid XIII/2b, 95 Alkyl- -chloride XIII/9a, 448 Alkylperoxy-organo- E13/1 v 196 (Salzbildung)... 

Couplings between alkenyl chlorides and alkyl Grignard reagents are catalyzed best by nickel complexes,as exemplified by the synthesis of terminal alkenes, disubstituted alkenes, cyclic alkenes and a silylmethyldiene (equations 5-8),2 while Pd(PPh3)4 has also been claimed to be useful for a few... 

Substituted 2-(morpholinocarbonyl)-6-(trifluoromethyl)furo[3,2-Z)]indole derivatives (341) have been obtained by the reaction of (340) with acyl chlorides, alkyl halides and alkenyl halides under basic conditions (Equation (7)) <86JMC2284>. 

Coupling of arylmagnesium halides takes place with aryl, alkenyl, and alkyl halides. Reaction of electron-rich chlorides can be carried out using carbene ligand XVI-2. For example, the coupling product of 4-chloroanisole (2) with phenylmag-nesium bromide (1) was obtained in high yield at room temperature [65]. Also... 

In a similar way, iminoalkynes containing aryl, alkenyl, and alkyl substituents undergoes Cul-catalyzed cyclization in excellent yields and short reaction times to give isoquinolines, pyridines, and pyrroles via a cycloisomerization (eq 18)4 Copper chloride is preferred, however, for the conversion of cyclic alkynyl imines to pyrrole-containing heterocycles. Copper iodide catalyzes the formation of furans from alkynyl ketones. ... 

Mercuration. Mercury(II) salts react with alkyl-, alkenyl-, and arylboranes to yield organomercurials, which are usehil synthetic intermediates (263). For example, dialkyhnercury and alkyhnercury acetates can be prepared from primary trialkylboranes by treatment with mercury(II) chloride in the presence of sodium hydroxide or with mercury(II) acetate in tetrahydrofuran (3,264). Mercuration of 3 -alkylboranes is sluggish and requires prolonged heating. Alkenyl groups are transferred from boron to mercury with retention of configuration (243,265). 

Chloroacylation of terminal aryl, alkyl or alkenyl alkynes [Le. the addition of RC(=0)-C1 across the CC triple bond] with aromatic acyl chlorides was catalysed by [IrCl(cod)(lPr)] (5 mol%) in good conversions (70-94%) in toluene (90°C, 20 h). Z-addition products were observed only, hitemal alkynes were umeactive. Surprisingly, a phosphine/[lr(p-Cl)(l,5-cod)]2 system under the same conditions provides decarbonylation products (Scheme 2.34) [117]. 

A wide range of A-acylbenzotriazoles 915 have been prepared under mild conditions in reactions of carboxylic acids with thionyl chloride in the presence of fourfold excess of benzotriazole, including R = alkyl, a-haloalkyl, a-alkoxyalkyl, alkenyl, alkinyl, aryl, and heteroaryl <2003S2795, 2004RQM275>. They represent convenient acylating agents for variety of nucleophiles. Synthetic applications of such compounds have been reviewed <2005SL1656>. 

Carbon monoxide rapidly inserts into the carbon—zirconium bond of alkyl- and alkenyl-zirconocene chlorides at low temperature with retention of configuration at carbon to give acylzirconocene chlorides 17 (Scheme 3.5). Acylzirconocene chlorides have found utility in synthesis, as described elsewhere in this volume [17]. Lewis acid catalyzed additions to enones, aldehydes, and imines, yielding a-keto allylic alcohols, a-hydroxy ketones, and a-amino ketones, respectively [18], and palladium-catalyzed addition to alkyl/aryl halides and a,[5-ynones [19] are examples. The acyl complex 18 formed by the insertion of carbon monoxide into dialkyl, alkylaryl, or diaryl zirconocenes may rearrange to a r 2-ketone complex 19 either thermally (particularly when R1 = R2 = Ph) or on addition of a Lewis acid [5,20,21]. The rearrangement proceeds through the less stable... 

Access to non-terminal ( ,2)-dienes and ( ,Z, )-trienes 61 is provided analogously through deprotonation of ( , )-4-alkyl-l-chloro-l,3-butadienes followed by insertion of the resultant carbenoid 60 into alkyl- and alkenyl-zirconocene chlorides (Scheme 3.14) [38], The corresponding internal (Z,Z)-dienes and (Z,Z, )-trienes are also readily obtained by insertion of (3-alkynyl carbenoids 62 [44] into alkyl- and alkenylzirconocene chlorides, respectively (Scheme 3.14). Reduction of the triple-bond moiety in the products 63 to afford the cis-alkenes is well known [45—47]. 

---