Matsuda–Heck arylation of itaconates: a versatile approach to heterocycles from a renewable resource

Abstract

Itaconic acid esters and hemiesters undergo Pd-catalyzed coupling reactions with arene diazonium salts in high to excellent yields. The coupling products of ortho-nitro arene diazonium salts can be converted in...

Development of a continuous flow synthesis of FGIN-1-27 enabled by in-line 19F NMR analyses and optimization algorithms

“…Facing these unexpected results, we reasoned that the high lability of the fluorine atom of diazonium salt 2 required the use of a non-nucleophilic solvent as recently demonstrated by Schmidt et al 28 In this frame, we reevaluated our flow process by switching the solvent from MeOH to THF which is known to be a suitable solvent for diazonium salt synthesis (Fig. 3).…”

Reactivity Patterns of Olefins in the Matsuda‐Heck‐Reaction and their Impact on the Formation of Pd‐Nanoparticles

“…While in the case of the methyl methacrylate another methyl group is present in the α‐position, the dimethyl itaconate with the additional methylene carboxy functionality has another polar group that would be capable of further complexation in the catalytic cycle. Itaconic acid derivatives have attracted increased interest from experts due to their synthetic potential as olefin components in the Matsuda‐Heck reaction [18,23,24] . When looking at the respective values in Table 1 and the reaction courses in Figure 1, it was noticeable that the acrylate derivatives, which carried an additional substituent in the α‐position, were clearly less reactive and, in addition, were characterized by significantly longer initial times.…”

“…Itaconic acid derivatives have attracted increased interest from experts due to their synthetic potential as olefin components in the Matsuda-Heck reaction. [18,23,24] When looking at the respective values in Table 1 and the reaction courses in Figure 1, it was noticeable that the acrylate derivatives, which carried an additional substituent in the αposition, were clearly less reactive and, in addition, were characterized by significantly longer initial times. Thus, the catalytic activity of the methyl methacrylate was 37 times lower than in the case of the methyl acrylate (entry 2 vs. entry 1).…”

Clinical Efficacy of Endoscopic Infratentorial Supracerebellar Approach for Pineal Region Tumors: A Retrospective Case‐Control Study

“…The implementation of neuroendoscopy via infratentorial supracerebellar approach also requires the adequate exposure of the transverse sinus and sinus confluence. If necessary, the sinus confluence and transverse sinus should be pulled upward to enlarge the surgical space [ 15 ]. The partial bridging veins of the superior vermis vein group can be selectively severed to obtain the best surgical field.…”