Alkenes, arenes, and heteroarenes possessing an 8-quinolylamide group as the directing group are alkylated with primary and secondary alkyl tosylates, mesylate, and halides in the presence of Fe(acac)3/diphosphine as a catalyst and ArZnBr as a base. The reaction proceeds stereospecifically for alkene substrates and takes place without loss of regiochemical integrity of the starting secondary tosylate, but with loss of the stereochemistry of the chiral center.

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DedicatedtoP rofessor Stephen L. Buchwald on the occasion of his 60th birthday.Supporting information for this article is availableonthe WWW under http://dx.doi.org/10.1002/adsc.201500276.Abstract: Alkenes and arenes possessing abidentate directing group are alkylated with ap rimary or secondary alkylzinc halide in the presence of an iron/ diphosphine catalyst and ad ichloroalkane oxidant. Acrylamides,i ncluding unsubstituted andm onosubstituted ones,r eact stereoselectively.U nder these reaction conditions, b-hydrogen elimination and homocoupling of the organometallic reagentare largely suppressed.T he reaction may proceed through C À Ha ctivation catalyzed by an organoiron(III) species.Keywords: alkylation;a mides; C À Ha ctivation; iron;z inc Alkylation of an alkene via transition-metal-catalyzed directedC À Hb ond activation [1] allowss tereospecific synthesisofs ubstituted olefins,b ut these reactions are often plagued by chemical ands tereochemical instability of the alkene substrate under C À Ha ctivation conditions.[2] Electrophilic alkylating reagents [3,4] have been mostly used for this purpose,b ut the scope of the alkene substrate is often limited.[2] Nucleophilic alkylating reagents have also received attention recently, [5] but one must overcomet heirf acile b-hydrogen elimination andh omocoupling in the presence of at ransition-metal catalyst. To date,t he use of these reagents has been limited to the alkylation of aromatic substrates, [6] such as palladium-catalyzed reactionof arenes with alkylboron [7] or -tin reagents [8] and the cobalt-catalyzed reaction of arenes with Grignard reagents, [9] and to the best of our knowledget here are no reports on the reaction of alkene substrates with nucleophilic alkylating reagents.W er eport here that an iron(III) salt [10] and ad iphosphinel igand catalyze the stereospecific alkylation of alkeneamides,i ncluding unsubstituted andm onosubstituted acrylamides with primary alkylzinch alides at 50-70 8 8C. Homocoupling and b-hydrogen elimination of the alkylmetal intermediates couldb el argely suppressed. Under the same reactionc onditions,a rene and heteroarene amides coulda lso be ortho alkylated with primary and secondary alkylzinc halides.We started our investigation with as ubstrate possessingamonodentated irecting group such as benzo[h]quinoline,w hich is known to react smoothlywith diarylzinc in the presence of an iron catalyst.[11] However, under similar conditions the reactiono ft his substrate with a b-hydrogen-possessing reagent such as phenethylzinc resulted mainly in the recovery of starting material, together with the formation of styrene (Supporting Information,( SI)). Based on our previous findingt hat ab identate8 -quinolylamideg roup [12] and an electron-accepting conjugated diphosphine can stabilize an organoiron species, [2b,d,13] we next investigated the reactiono faq uinolylamides ubstrate such as 1 with 2-phenethylzinc chloride in the presence of an iron/diphosphinec atalyst and am ild dichloroalkane oxidant (DCIB), [2d,11] to find tha...

A general, rapid, and efficient method for the copper-catalyzed Finkelstein reaction of (hetero)aromatics has been developed using continuous flow to generate a variety of aryl iodides. The described method can tolerate a broad spectrum of functional groups, including N-H and O-H groups. Additionally, in lieu of isolation, the aryl iodide solutions were used in two distinct multistep continuous-flow processes (amidation and Mg-I exchange/nucleophilic addition) to demonstrate the flexibility of this method.

We synthesised heteroleptic azadipyrrinato-dipyrrinato hybrid zinc(II) complex 1-Zn-2, by means of the stepwise coordination method. Homoleptic bis(azadipyrrinato)zinc(II) complex 1-Zn-1 was non-fluorescent, whereas 1-Zn-2 exhibited detectable fluorescence from azadipyrrinato ligand 1.