Suzuki-miyaura cross-coupling in acylation reactions, scope and recent developments

Abstract

Since the first report and due to its handiness and wide scope, the Suzuki-Miyaura (SM) cross coupling reaction has become a routine methodology in many laboratories worldwide. With respect to other common transition metal catalyzed cross couplings, the SM reaction has been so far less exploited as a tool to introduce an acyl function into a specific substrate. In this review, the various approaches found in the literature will be considered, starting from the direct SM acylative coupling to the recent developments of cross coupling between boronates and acyl chlorides or anhydrides. Special attention will be dedicated to the use of masked acyl boronates, alkoxy styryl and alkoxy dienyl boronates as coupling partners. A final section will be then focused on the acyl SM reaction as key synthetic step in the framework of natural products synthesis.

Scheme 1

Bumagin’s first carbon monoxide free carbonylation of arylboronic acids.

Scheme 2

Haddach’s carbonylation of arylboronic acids under anhydrous conditions.

Scheme 3

Urawa’s synthesis of ortho-cyanobenzophenone derivatives.

Scheme 4

Rolando’s approach to substituted chalcones derivatives by SM-coupling of cinnamyl boronic acids.

Scheme 5

Copper (I)-Pd(II) promoted carbonylation of arylboronic acids.

Scheme 6

Li’s imidazolium catalyst applied to the synthesis of diaryl ketones.

Scheme 7

Gooßen’s SM-coupling of arylboronic acids with anhydrides.

Scheme 8

Gooßen’s pivalic anhydride promoted coupling of arylboronic acids with carboxylic acids.

Scheme 9

Zhang’s coupling of arylboronic acids with anhydrides in the presence of additives.

Figure 1

Shao’s (left) and Wu’s (right) catalysts applied in the synthesis of aromatic ketones by Pd-catalyzed coupling of arylboronic acids with anhydrides.

Scheme 10

Pd/Cu catalyzed carboxylation and amidation of arylboronic acids derivatives.

Scheme 11

Takemoto’s Pd-catalyzed amidation of olefins via 9-BBN intermediates.

Scheme 12

Synthesis of Weinreb amides by SM-coupling of arylboronic acids/ organotrifluoro borates with N-methoxy-N-methyl-carbamoyl chloride.

Scheme 13

SM cross coupling of Methyl N-[Methoxy(methylthio)methylene]carbamate.

Scheme 14

Suzuki-Miyaura carbomethoxylation of alkenylborane derivatives.

Scheme 15

Alper’s Rh/Pd catalyzed carbomethoxylation of alkyl and vinyl bromides.

Scheme 16

Hypervalent iodonium salts promoted synthesis of chalcone derivatives.

Scheme 17

Andrus’s carbonylative coupling of aryl diazonium salts.

Scheme 18

Pd-catalyzed carbovinylation of lactam-derived triflates.

Figure 2

Alkoxydienyl and alkoxystyryl boronates.

Scheme 19

Synthesis of butadienyl boronic esters.

Scheme 20

SM coupling between alkoxy dienyl boronates and heterocycle derived triflates.

Scheme 21

Synthesis of tricarbocyclic derivatives.

Scheme 22

Synthesis of azepines.

Figure 3

Representation of some of the scaffolds that can be synthesized through SM coupling between heterocyles derived triflates or phosphates and alkoxydienyl boronates.

Scheme 23

Synthesis of spyrocyclic ketones.

Scheme 24

Synthesis of seven membered oxacycles.

Scheme 25

Coupling reactions between alkoxydienyl and alkoxystyrylboronates and azoles.

Figure 4

Naturally occurring strigol with reference compound GR 24 (left) and our target analogue (right).

Scheme 26

Retrosynthetic approach to SL’s ABC core through SM-coupling of dienyl boronate derivatives.

Scheme 27

SM coupling of dienyl boronates for the synthesis of strigolactones ABC core.

Scheme 28

Pd-catalyzed alkenylation of lactones and lactames applied to the synthesis of bicyclic SL’s analogues.

Scheme 29

Acylation of indolyl triflates applied to the synthesis of SL’s tricyclic core.

Scheme 30

Guy’s synthesis of thiosemicarbazone inhibitors.

Figure 5

Furanosteroid class of PI3-kinase inhibitors.

Scheme 31

Jacobi’s synthesis of furanosteroid viridin’s core.

Scheme 32

Beller’s two-steps synthesis of Suprofen.

Scheme 33

Synthesis of Combrestatin A4 analogues.

Scheme 34

Yang and Xue’s synthesis of heteroaryl-substituted pyridine derivatives.