2020
DOI: 10.1038/s41467-020-19717-6
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Abstract: Among the plethora of catalytic methods developed for hydrocarbofunctionalization of olefins to date, reactions that regioselectively install a functionalized alkyl unit at the 2-position of a terminal unactivated C=C bond to afford branched products are scarce. Here, we show that a Ni-based catalyst in conjunction with a stoichiometric reducing agent promote Markovnikov-selective hydroalkylation of unactivated alkenes tethered to a recyclable 8-aminoquinaldine directing auxiliary. These mild reductive process… Show more

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Cited by 56 publications
(27 citation statements)
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References 76 publications
(101 reference statements)
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“…However, longer alkyl chains required a longer chain walking distance and resulted in diminished yields and regioselectivities. Like the report by Koh and Yang, a 1:1:1:1 mixture of regioisomers resulted largely in single regioisomeric products (89:11 branched regioselectivity, 81% yield; 88:12 linear regioselectivity, 70% yield) on gram scale, offering a useful purification of inexpensive, unrefined chemical feedstocks.…”
Section: Recent Reports Of Ni-catalyzed Reactionsmentioning
confidence: 62%
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“…However, longer alkyl chains required a longer chain walking distance and resulted in diminished yields and regioselectivities. Like the report by Koh and Yang, a 1:1:1:1 mixture of regioisomers resulted largely in single regioisomeric products (89:11 branched regioselectivity, 81% yield; 88:12 linear regioselectivity, 70% yield) on gram scale, offering a useful purification of inexpensive, unrefined chemical feedstocks.…”
Section: Recent Reports Of Ni-catalyzed Reactionsmentioning
confidence: 62%
“…Koh, Yang, and co-workers reported a hydrofunctionalization system that uses alkyl halides as well as a recyclable 8aminoquinaldine directing auxiliary, which coordinates to nickel and facilitates the challenging 2-selective functionalization of unactivated terminal alkenes. 53 The alkyl halides were used as both a hydride source (via β-hydride elimination) and an alkyl source, as demonstrated by thorough mechanistic studies. The authors attribute the exceptional selectivity to the ligand's o-methyl substituent, which induces additional strain facilitating alkene dissociation and subsequent Ni−alkyl βhydride elimination instead of promoting migratory insertion and alkyl installation onto the 1-position (Scheme 19).…”
Section: ■ Recent Reports Of Ni-catalyzed Reactionsmentioning
confidence: 99%
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“… 1 The transformation can forge two new C–C or C–X bonds for installing two different components into the C–C double bonds, which has aroused tremendous interest from many research groups. For the more difficult difunctionalization of unactivated alkenes, in recent years, the Engle group and others have developed a series of transition-metal-catalyzed alkene 1,2-difunctionalization reactions with the assistance of the 8-aminoquinoline (AQ) auxiliary as a strongly coordinating bidentate directing group, including hydrofunctionalization, 2 dicarbofunctionalization, 3 carboamination, 4 carboboration and aminoboration, 5 and so on ( Scheme 1a ). In most cases of the above transformations, the nucleopalladated alkylpalladium( ii ) species stabilized by a bidentate directing group were initially generated, and then protodepalladation or oxidative addition with electrophiles occurred to afford the difunctionalizated products.…”
Section: Introductionmentioning
confidence: 99%
“…Hydrofunctionalization reactions of alkenes are a valuable synthetic tool and, accordingly, have been studied extensively in recent decades. This class of reactions consists of the addition of an element–hydrogen bond across a carbon–carbon double bond (Scheme ). Prominent examples of hydrofunctionalization reactions for olefins include hydroboration, , hydrosilylation, ,, hydroamination, hydroalkoxylation, , and hydrocarbonation. ,, Intriguingly, some examples of hydrofunctionalization reactions, specifically hydroboration, hydrophosphination, and hydroamination, have recently been realized for boron–boron double and triple bonds by Braunschweig and co-workers. …”
Section: Introductionmentioning
confidence: 99%