Allylic derivatives allyl-aryl coupling

The reaction of (4-benzenesulfonylphenyl) benzylsulfoxide (91) with allylmagnesium halide afforded only the benzyl derived ligand coupling product (69), without any allyl-aryl coupling product. 

Protection of allylic amines with a f-butoxycarbonyl (Boc),benzyloxycar-bonyl (Cbz), or p-methoxybenzyloxycarbonyl (PMB) group furnished the desired 9-BBN derivative for the coupling reaction [106, 107, 119]. The alkyl-vinyl and alkyl-aryl coupling reactions readily proceed on the solid-phase which was demonstrated in the preparation of members of several structurally distinct PG classes (47) [120]. 

I copper can be prepared by reduction )th lithium naphthalcnidc under argon, dides at 0-25° to form organocopper rmed undergoes self-coupling almost X derived from aryl and alkynyl halides arc reduced to ArH. These arylcopper d chlorides and allylic and benzylic... 

Allyl silanes react with epoxides, in the presence of Bp3 OEt2 to give 2-allyl alcohols.The reaction of a-bromo lactones and CH2=CHCH2Si(SiMe3)3 and AIBN leads to the a-allyl lactone.On the other hand, silyl epoxides have been prepared from epoxides via reaction with iec-butyllithium and chlorotri-methylsilane. ° a-Silyl-A-Boc-amines were prepared in a similar manner from the A-Boc-amine. " Arylsilanes were prepared by reaction of an aryl-lithium intermediate with TfOSi(OEt)3. In the presence of BEs etherate, allyl silane and a-methoxy A-Cbz amines were coupled. Benzyl silanes coupled with allyl silanes to give ArCHa—R derivatives in the presence of VO(OEt)Cl2 " and allyltin compounds couple with allyl silanes in the presence of SnCl4. Allyl silanes couple to the a-carbon of amines under photolysis conditions. 

Dienes and allylarcncs can be prepared by the Pd-catalyzcd coupling of allylic compounds with hard carbon nucleophiles derived from alkenyl and aryl compounds of main group metals. Allylic compounds with various leaving groups can be used. Some of them are unreactive with soft nucleophiles, but... 

Table 6. Ni-bpy catalyzed electroreductive cross-coupling between aryl halides and vinylic or allylic derivatives...

Mowery and DeShong reported on the use of siloxanes 72 (Figure 16) as versatile transmetallation agents for Pd(dba)3-catalyzed couplings with aryl halides and allylic alcohol derivates, in the presence of TBAF and at high temperature (95 They later used aryl silatrane 73 (Figure 16) as a suitable partner for the fluoride-promoted... 

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