Development of a Safe and Scalable Process for the Preparation of Allyl Glyoxalate

Abstract

While conversion of dialkyl tartrate esters to the corresponding glyoxalic acid esters has been well-documented, large scale application of some common laboratory protocols presents a myriad of challenges. The low cost, high availability, and predictable reactivity of sodium periodate make it an attractive choice for synthetic chemistry applications; the resulting solid byproducts, however, have a high thermal potential and therefore must be handled with care during cleanup and disposal, especially on large scale. Successful demonstration of the synthesis of glyoxaldehydes by oxidative cleavage of tartrate esters with sodium periodate is discussed herein. Furthermore, this account describes the process safety/engineering investigation carried out to ensure a robust and safe process for the scale manufacture of allyl glyoxalate via sodium periodate-mediated cleavage of diallyl tartrate.

Zidovudine-β-Lactam Pronucleoside Strategy for Selective Delivery into Gram-Negative Bacteria Triggered by β-Lactamases

“…To prepare intermediates 16a–f , the nitrogen atom has to be condensed on the glyoxalate moiety. The allyl group on the ester function as the PG has been chosen, and the corresponding glyoxalate reagent was prepared in two steps according to the literature method . Hydroxyl intermediates 16a–f can be purified or directly engaged in the next step.…”

“…The allyl group on the ester function as the PG has been chosen, and the corresponding glyoxalate reagent was prepared in two steps according to the literature method. 53 Hydroxyl intermediates 16a−f can be purified or directly engaged in the next step. The acylation reaction was performed by acetic anhydride to give the corresponding To introduce the N-acyl side chain, the carboxylic acid function of the corresponding substituent was activated by the EDCI/ HOBt mixture and then condensed on amino compound 18 to provide conjugates 17g−h.…”

Pyridylidene Amide Ru Complex for Selective Oxidation in Organic Synthesis

“…10 While ozone is inconvenient as the terminal oxidant due to its hazardous properties, NaIO 4 constitutes a suitable alternative 11 that is also potentially applicable for large scale preparations. 12 Considering the ultrahigh efficiency of complex 1 containing a bis-pyridylideneamide (bis-PYA) ligand in catalyzing olefin oxidation (Figure 1), 13 we were interested in exploiting its activity toward other functional groups and in particular toward sulfides to access highly valuable agrochemical and pharmaceutical sulfone intermediates. Here, we demonstrate that this complex is a potent catalyst for the selective oxidation of sulfides to sulfones, even in the presence of other oxidizable functional groups.…”

“…A general challenge in the preparation of sulfones from sulfides is often the incomplete oxidation. , Full oxidation has been achieved with carbon nanotubes-Ru and NaIO 4 and with different high-valent molybdenum systems and organocatalyzed with the use of ozone . While ozone is inconvenient as the terminal oxidant due to its hazardous properties, NaIO 4 constitutes a suitable alternative that is also potentially applicable for large scale preparations …”

Cyclocarbonylation of Allenyl Glyoxylate Strategy to Build the Tricyclic Core of Cyclocalopin A

“…For example, the Kornblum procedure for the conversion of 5 to 4 by a four-step sequence ((i) BrCH 2 COBr, (ii) NaI, (iii) AgNO 3 , (iv) NaOAc) turned out to be unpromising, resulting in decomposition upon attempted isolation. Only modification of an oxidative cleavage of allenyl tartarate derived from 5 provided allenyl glyoxylate 4 in a fairly pure form . We adapted the optimal conditions with the racemic homoallenyl alcohol (±)- 5 obtained through the Johnson–Claisen rearrangement followed by LAH reduction (79%, two steps).…”