Palladium‐Catalyzed Three‐Component Coupling Reaction of Allyl Carboxylates, Norbornenes and Diboronates Involving Sequential Olefins Insertion and Borylation Reaction

Abstract

Summary of main observation and conclusion An efficient Pd‐catalyzed three‐component coupling reaction of allyl carboxylates, norbornenes and diboronates is described, which allows efficient assembly of C(sp3)—C(sp3) and C(sp3)—B bonds in a single process. Moreover, this approach shows advantages of good chemo‐ and regioselectivity, as well as good substrates suitability.

Palladium-Catalyzed Stereoselective Difunctionalization of Bicyclic Alkenes with Organoammonium Salts and Organoboronic Compounds

“…On the basis of previous literature, ,− , a plausible reaction pathway was proposed (Scheme ). The Pd(0) catalyst was first added to organoammonium salts to afford intermediate A with release of NMe 3 .…”

“…The Pd(0) catalyst was first added to organoammonium salts to afford intermediate A with release of NMe 3 . A then underwent syn -addition with bicyclic alkenes, generating intermediate B . ,,− In the presence of a base, transmetalation of B with arylboronic acid occurred to afford intermediate C . Finally, reductive elimination of C produced the target product and regenerated the Pd(0) complex to complete the catalytic cycle.…”

“…13 C{ 1 H} NMR (100 MHz, CDCl 3 ): δ 157. 5,138.9,135.5,133.9,131.9,129.4,128.7,126.9,126.3,125.5,125.3,125.2,124.1,113.5,55.3,51.2,49.3,42.8,39.5,35.3,34.9,31.1,29.1. HRMS O, 342.1984; found, 342.1976.…”

“…In recent years, many excellent works have been reported, while most of these transformations were conducted on the basis of aryl halides as electrophiles (Scheme a). − From the economic and sustainable point of view, the use of chemicals readily available in nature instead of organohalides as electrophiles in organic synthesis is more attractive . In this respect, Jiang et al developed an efficient Pd-catalyzed carboboration reaction of norbornenes with allyl carboxylates and diboronates (Scheme b) . Stanley and co-workers reported a Ni-catalyzed intermolecular cis -selective carboacylation of norbornenes and tetraarylborates with imide as electrophiles (Scheme c) .…”

“…4 In this respect, Jiang et al developed an efficient Pd-catalyzed carboboration reaction of norbornenes with allyl carboxylates and diboronates (Scheme 1b). 5 Stanley and co-workers reported a Ni-catalyzed intermolecular cis-selective carboacylation of norbornenes and tetraarylborates with imide as electrophiles (Scheme 1c). 6 Very recently, a Pd-catalyzed trans-selective carboacylation of alkenes with ester electrophiles and tetraarylborates was also reported by the Stanley group (Scheme 1d).…”