Rhodium-catalyzed hydroformylation in γ-valerolactone as a biomass-derived solvent

Towards Sustainable C−H Functionalization Reactions: The Emerging Role of Bio‐Based Reaction Media

“…In recent years, GVL has been used in several transition metal catalyzed processes such as, among others, the palladium‐catalyzed Hiyama, Mizoroki–Heck and Sonogashira cross‐coupling reactions, platinum‐ and rhodium‐catalyzed hydroformylations and palladium‐catalyzed aminocarbonylation reactions . In some cases, the use of GVL in combination with a heterogeneous palladium catalyst resulted in additional benefits, such as limited metal leaching, compared to the use of traditional dipolar aprotic media …”

“…For these reasonsGVL has been proposed as a"greener"alternative to these petroleum-derived and generally toxic solvents that, despite their highly unfavorable sustainability profile, still find wide use in organic synthesis. [21] In recent years, GVL has been used in severalt ransition metal catalyzed processes such as, among others, the palladium-catalyzed Hiyama, [23] Mizoroki-Heck [24] and Sonogashira [25] cross-coupling reactions, platinum- [26] and rhodium-catalyzed [27] hydroformylations andp alladium-catalyzed aminocarbonylation reactions. [28] In some cases, the use of GVL in combination with ah eterogeneous palladium catalyst resulted in additional benefits, such as limited metal leaching, compared to the use of traditional dipolar aproticm edia.…”

Conservative evolution and industrial metabolism in Green Chemistry

“…The 13 C 5 -GVL derived from 13 C 6 -fructose with an overall yield of 55% and the GVL solvent was distinguished with ease using a 13 C-labelling technique. GVL can also be successfully utilized as a reaction medium for the homogeneous Pt-(Scheme 15) and Rh-catalyzed enantioselective hydroformylation of styrene, 67,68 as well as the Pd-catalyzed aminocarbonylation (Scheme 16) of iodoaromatic compounds. 69 In general, slightly lower activities were observed in GVL compared to in conventional organic solvents, however, the selectivities were similar, allowing its application as an alternative reaction environment.…”

Immobilization of Rh(I)-N-Xantphos and Fe(II)-C-Scorpionate onto Magnetic Nanoparticles: Reusable Catalytic System for Sequential Hydroformylation/Acetalization

“…Nowadays, one of the ultimate goals for synthetic chemists is to mimic natural systems for the construction of complex molecules using sequential catalysis [1][2][3]. Catalytic hydroformylation has been used as a central reaction in several sequential processes to produce high-value products directly from olefins, such as alcohols, acetals, amines, and others [4][5][6][7][8][9][10][11]. We highlight the hydroformylation/acetalization reaction that allows the direct transformation of olefins into high-value oxygenated products in a sequential process without isolation of the aldehyde intermediates [12][13][14][15][16][17], including in the valorization of terpenes [18,19].…”