Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates

Zhou, Yujing; Bandar, Jeffrey S.; Buchwald, Stephen L.

doi:10.1021/jacs.7b04937

Cited by 86 publications

(49 citation statements)

References 65 publications

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“…Furthermore, Buchwald and co-workers have developed a copper-catalyzed hydroacylation reaction of alkenyl arenes with anhydrides [17] and more recently carboxylic acids. [18] Herein, a method is presented for the borylacylation of a variety of activated alkenes with widely available acid chlorides (Scheme 1C). [19] …”

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confidence: 99%

“…[16] While this is as ignificant advance,inour view,the direct synthesis of ketones from simple and widely available precursors would be valuable to streamline synthesis.Furthermore,Buchwald and co-workers have developed ac opper-catalyzed hydroacylation reaction of alkenyl arenes with anhydrides [17] and more recently carboxylic acids. [18] Herein, am ethod is presented for the borylacylation of av ariety of activated alkenes with widely available acid chlorides (Scheme 1C). [19] Initial studies focused on the use of thioester-derived electrophiles in aFukuyama-type cross-coupling.…”

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Copper‐Catalyzed Borylacylation of Activated Alkenes with Acid Chlorides

2017

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A method for the copper-catalyzed borylacylation of activated alkenes is presented. The reaction involves borylcupration of the alkene, followed by capture of the generated alkyl–copper intermediate with an acid chloride. The reactions operated with low catalyst loading and generally occurre within 15 min at room temperature for a range of activated alkenes. In the case of vinyl arenes, enantioselective borylacylation was possible.

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Copper‐Catalyzed Borylacylation of Activated Alkenes with Acid Chlorides

2017

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“…While this is a significant advance, in our view, the direct synthesis of ketones from simple and widely available precursors would be valuable to streamline synthesis. Furthermore, Buchwald and co‐workers have developed a copper‐catalyzed hydroacylation reaction of alkenyl arenes with anhydrides and more recently carboxylic acids . Herein, a method is presented for the borylacylation of a variety of activated alkenes with widely available acid chlorides (Scheme C) …”

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confidence: 99%

Copper‐Catalyzed Borylacylation of Activated Alkenes with Acid Chlorides

2017

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Amethod for the copper-catalyzed borylacylation of activated alkenes is presented. The reaction involves borylcupration of the alkene,f ollowed by capture of the generated alkyl-copper intermediate with an acid chloride.The reactions operated with low catalyst loading and generally occurre within 15 min at room temperature for arange of activated alkenes.In the case of vinyl arenes,e nantioselective borylacylation was possible.

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“…[4,5] Catalytic in situ generation of nucleophilic organometallic speciesb yi nsertiono fu nsaturated CÀCb onds to MÀXb onds followed by trapping with acyl electrophiles affords attractive synthetic methods, which can avoid the use of stoichiometric amountso fp re-formed organometallic reagents. [6] Metal-catalyzed reductivec ouplingo fC ÀCu nsaturated compounds with electrophiles is representative. [7,8] For acylation,c arboxylic anhydrides were used as acylating electrophiles in the reactiono f vinylarenes in the presence of hydrosilanes or H 2 as H sources.…”

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Nickel‐Copper‐Catalyzed Hydroacylation of Vinylarenes with Acyl Fluorides and Hydrosilanes

Ueda

Iwai

Sawamura

2019

Chemistry A European J

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The hydroacylation of vinylarenesw ith acyl fluorides and hydrosilanes was enabled by as ynergistic bimetallic Ni/Cu-catalytic system, giving access to the corresponding branched ketone products. The reaction takes place under mild conditions at 25-80 8Ca nd tolerates base-sensitive functional groups such as methoxycarbonyl and acetoxy groups.Acyl fluorides, which are easily preparedf rom carboxylic acids, [1] are less common as acylatingr eagents than the corresponding chlorides and bromides due to their inertness as acylating reagents under conventional conditions. However,t he use of acyl fluoridesa sr eagents in organic synthesis through activation of the CÀFb ond have attracted growing interest in recent years, offering new types of molecular transformations that have not been achieved with acyl chlorideso rb romides. Generally,t he fluorides show better tolerance towards nucleophilic or basic functional groups than the chlorides and bromides.Apioneering work by Rovis described an efficient ketone synthesis through Ni-catalyzed cross-coupling of acyl fluorides with organozincs( Scheme 1a). [2] Later,O giwaraa nd Sakai reported similart ransformationsu sing organosiliconso r organoborons by Pd catalysis. [3] These reactions were initiated by oxidativea ddition of the acyl C(sp 2 )ÀFb onds to low-valent metal complexes,producing acyl metal intermediates. [4,5] Catalytic in situ generation of nucleophilic organometallic speciesb yi nsertiono fu nsaturated CÀCb onds to MÀXb onds followed by trapping with acyl electrophiles affords attractive synthetic methods, which can avoid the use of stoichiometric amountso fp re-formed organometallic reagents. [6] Metal-catalyzed reductivec ouplingo fC ÀCu nsaturated compounds with electrophiles is representative. [7,8] For acylation,c arboxylic anhydrides were used as acylating electrophiles in the reactiono f vinylarenes in the presence of hydrosilanes or H 2 as H sources. [6a, 7a,b] More recently,G agosz and Riant used acyl fluorides as acylating reagents for the Cu-catalyzed boroacylation of alleneswith bis(pinacolato)diboron (Scheme 1b). [9] Our long-standing interest in synergistic bimetallic catalysis prompted us to explore the possibility of enabling the hydroacylation of vinylarenes with acyl fluorides and hydrosilanes by synergistic Ni/Cu two-metal catalysis. [10][11][12][13][14][15] As shown in Scheme 1c,a na cyl fluoridei sa ctivated through oxidative addition to aN i(0) complex (step a). Concurrently,avinylarene is converted into an ucleophilic alkylcopper speciesb yi nsertion into aC u ÀHs pecies( hydrocupration, step d) [16] that is generated in situ from aC u ÀFs peciesw ith ah ydrosilane (step e). [17] The two catalytic speciesm eet and transmetalation occurs to give the corresponding diorganonickel(II) complex with simultaneous regeneration of the CuÀFs pecies (step b). Finally,r e-[a] Prof. Dr.M.S awamura Institute for Chemical Reaction Design and Discovery (WPI-ICReDD)

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Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates

Cited by 86 publications

References 65 publications

Copper‐Catalyzed Borylacylation of Activated Alkenes with Acid Chlorides

Copper‐Catalyzed Borylacylation of Activated Alkenes with Acid Chlorides

Copper‐Catalyzed Borylacylation of Activated Alkenes with Acid Chlorides

Nickel‐Copper‐Catalyzed Hydroacylation of Vinylarenes with Acyl Fluorides and Hydrosilanes

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