The Divergent Reactivity of Acid Chlorides Under Transition Metal Catalysis

Abstract

The power and ability of catalysis to build multiple C-C bonds in a single step has had a transformative impact on organic synthesis. While the reactivity of organohalides with metal catalysts is widely appreciated, the related and more intricate reactivity of acid chlorides is less so, despite their use as common reagents in synthesis. Here, we review the transformations of acid chlorides in combination with unsaturated C-C bonds catalyzed by palladium, rhodium, or iridium and provide an outlook for future research opportunities.

Keywords: Acid chlorides; Catalysis; C−C bond formation; Iridium; Palladium; Rhodium.

Figure 1

Transformations that can be achieved by combining acid chlorides and unsaturated C−C bonds under palladium, rhodium, and iridium catalysis.

Scheme 1

Tsuji's discovery on the reactivity of acid chlorides with styrene.

Scheme 2

Chiusoli's palladium‐catalyzed acylative coupling of acid chlorides and acrylates.

Scheme 3

Hallberg's acylative coupling of aroyl chlorides and vinyl ethers.

Scheme 4

Takaishi's acylative coupling of norbornoyl chloride with styrene.

Scheme 5

Chloroacylation reactions of terminal alkynes developed by Tanaka.

Scheme 6

Tsuji's chloroacylation of terminal alkynes with aroyl chlorides.

Scheme 7

Tsuji's palladium‐catalyzed chloroacylation with alkyl acid chlorides. Cy=cyclohexyl.

Scheme 8

Tsuji's 1,4‐acylative silylation of 1,3‐dienes.

Scheme 9

Miura's rhodium‐catalyzed acylative arylation, with the acid chloride serving as both the aryl and acyl source.

Scheme 10

Cheng's suite of conditions to realize the 1,2‐acylative borylation, silylation, or stannylation of allenes.

Scheme 11

Ueno's hydroacylation of acrylates.

Scheme 12

Tsuji's palladium‐catalyzed hydroacylation of allenes.

Scheme 13

Tsuji's acylative arylation of allenes utilizing acid chlorides and boronic acids.

Scheme 14

Miura's chloroarylation of terminal alkynes involves the excision of a carbon monoxide unit embedded within the acid chloride.

Scheme 15

Miura's indenone synthesis resulting from the rhodium‐catalyzed reaction of aroyl chlorides and internal alkynes.

Scheme 16

Miura's rhodium‐catalyzed indanone synthesis achieved by combining acid chlorides and norbornenes.

Scheme 17

Tsuji's iridium‐catalyzed chloroarylation of terminal alkynes.

Scheme 18

Carboformylation of internal alkynes reported by Morandi.

Scheme 19

Palladium‐catalyzed three‐component coupling to prepare cyclopentenones from α,β‐unsaturated acid chlorides, and internal alkynes reported by Morandi.

Scheme 20

Palladium‐catalyzed decarbonylative Mizoroki–Heck reaction of aroyl chlorides and acrylates.

Scheme 21

Spencer's developments in the palladium‐catalyzed Mizoroki–Heck coupling of aroyl chlorides and alkenes. (A) Coupling aroyl chlorides with disubstituted alkenes. (B) Combing aroyl chlorides and ethene to prepare styrene or stilbenes. (C) Leveraging the different reactivity of aroyl chlorides and aryl bromides to chemoselectively prepare unsymmetrical divinylbenzenes.

Scheme 22

Decarbonylative Mizoroki–Heck coupling of aroyl chlorides with vinyl ethers.

Scheme 23

Cabri's α‐selective coupling of aroyl chlorides with vinyl ethers.

Scheme 24

Preparation of trienes using the palladium‐catalyzed Mizoroki–Heck reaction reported by Kasahara.

Scheme 25

Miura's base‐free Mizoroki–Heck reaction. (A) Rhodium‐catalyzed reaction. (B) Palladium‐catalyzed reaction.

Scheme 26

Application of the decarbonylative Mizoroki–Heck reaction towards the synthesis of 4′‐resveratol esters.

Scheme 27

Evaluating the Mizoroki–Heck coupling of acid chlorides for polymerization.

Scheme 28

Three‐component coupling of aroyl chlorides, norbornene, and tributyl vinylstannane.

Scheme 29

Palladium‐catalyzed 1,4‐carbosilylation of 1,3‐dienes.

Scheme 30

Synthesis of substituted naphthalenes through the annulation of aroyl chlorides and internal alkynes.

Scheme 31

Miura's use of biphenyl acid chlorides and alkynes to prepare phenanthrene derivatives.

Scheme 32

Palladium‐catalyzed carbochlorocarbonylation of norbornadiene and norbornene with acid chlorides.