trans-Chloro(1-Naphthyl)bis(triphenylphosphine)nickel(II)/PCy₃ Catalyzed Cross-Coupling of Aryl and Heteroaryl Neopentylglycolboronates with Aryl and Heteroaryl Mesylates and Sulfamates at Room Temperature

Abstract

trans-Chloro(1-naphthyl)bis(triphenylphosphine)nickel(II) complex/PCy(3) system has been successfully applied as catalyst for the Suzuki-Miyaura cross-coupling of aryl and heteroaryl neopentylglycolboronates with aryl and heteroaryl mesylates and sulfamates in THF at room temperature. This cross-coupling reaction tolerates various functional groups, including keto, imino, ester, ether, and cyano. Together with the nickel-catalyzed, one-pot, two-step neopentylglycolborylation, this bench stable and inexpensive Ni(II)-based catalyst can be utilized as an alternative to Ni(COD)(2)/PCy(3) to provide an inexpensive, robust, and convenient synthesis of biaryl and heterobiaryl compounds.

Suzuki–Miyaura coupling reactions of aryl chlorides catalyzed by a new nickel(II) σ‐aryl complex

“…3) in all reactions of phenylboronic acid with various aryl chlorides and other side products (7b-g, Fig. [28] Except for compound 7 g, these side products are known and their spectral data are consistent with those in the literature. This activation process is also consistent with that reported by Percec.…”

“…This precatalyst works [46] 2 p-F-Ph-Cl p-F-Ph-Ph-p-OMe 91 [45] 3 p-MeO 2 C-Ph-Cl p-MeO 2 C-Ph-Ph-p-OMe 96 [28] 4 o-MeO 2 C-Ph-Cl o-MeO 2 C-Ph-Ph-p-OMe 92 [28] 5 p-NC-Ph-Cl p-NC-Ph-Ph-p-OMe 68 [28] 6 p-OHC-Ph-Cl p-OHC-Ph-Ph-p-OMe 85 [24] a Reaction conditions: aryl chloride (1.0 mmol), p-methoxyphenylboronic acid (1.2 mmol), precatalyst 1 (0.05 mmol), PPh 3 (0.10 mmol), K 2 CO 3 (3.0 mmol), toluene (3 ml). This precatalyst works [46] 2 p-F-Ph-Cl p-F-Ph-Ph-p-OMe 91 [45] 3 p-MeO 2 C-Ph-Cl p-MeO 2 C-Ph-Ph-p-OMe 96 [28] 4 o-MeO 2 C-Ph-Cl o-MeO 2 C-Ph-Ph-p-OMe 92 [28] 5 p-NC-Ph-Cl p-NC-Ph-Ph-p-OMe 68 [28] 6 p-OHC-Ph-Cl p-OHC-Ph-Ph-p-OMe 85 [24] a Reaction conditions: aryl chloride (1.0 mmol), p-methoxyphenylboronic acid (1.2 mmol), precatalyst 1 (0.05 mmol), PPh 3 (0.10 mmol), K 2 CO 3 (3.0 mmol), toluene (3 ml).…”

“…However, Ni(COD) 2 and the phosphine ligand PCy 3 are expensive and air-sensitive. [28] As part of our research interest in the catalytic activities of transition metal complexes, we prepared a new Ni(II) s-aryl complex, trans-chloro (9-phenanthrenyl)bis(triphenylphosphine)nickel(II) (1) (Fig. [26] Meanwhile, Yang reported a readily available and air-stable Ni(II) s-aryl complex as an efficient precatalyst for the Suzuki-Miyaura reactions of aryl halides and sulfonates.…”

Well-defined nickel and palladium precatalysts for cross-coupling

“…These results were extended by Mizojiri et al 92,93 who showed that non-classical electrophiles, including aryl mesylates, tosylates and allyl carbonates, could be coupled with lithium arylborates under mild conditions with [(PPh 3 ) 2 NiCl 2 ]. Recently, Percec and co-workers 89,94 demonstrated that [(PPh 3 ) 2 NiCl 2 ] can effectively perform Suzuki–Miyaura reactions with both pseudohalides and phenol derivatives, such as sulfamates and carbamates, which can be used as directing groups in C–H functionalization reactions. Other non-classical electrophiles that can be used in coupling reactions with this precatalyst include 1,3-disubstituted secondary allylic carbonates in Suzuki–Miyaura reactions 95 and amides in Negishi reactions 96 .…”

“…Despite this seminal work, there were relatively few additional reports describing the use of σ -aryl complexes as precatalysts for cross-coupling until the late 2000s. Since then, both the Yang and Percec laboratories have shown [(PCy 3 ) 2 Ni(1-naphthyl)Cl] to be an efficient precatalyst for Suzuki–Miyaura reactions involving aryl halides 145 , tosylates 145,146 , sulfonates 145 , sulfamates 94 and mesylates 94 . In fact, [(PCy 3 ) 2 Ni(1-naphthyl)Cl] is able to promote Suzuki–Miyaura coupling of aryl sulfamates with neopentylglycolboronates at room temperature 147 .…”