Recent Advances in ADMET Chemistry

A Catalytic Approach to (R)‐(+)‐Muscopyridine with Integrated “Self‐Clearance”

“…This reflects the greater ease of formation of the 13-membered ring as compared to the kinetically and thermodynamically handicapped 11-membered analogue that would derive from 10 by ring-closing metathesis (RCM). [15,16] After most of the solvent has been distilled off, however, residual 10 is forced to polymerize by acyclic diene metathesis (ADMET) [17] and thereby completely disappears from the GC trace while the macrocycle persists. Evidently, the indenylidene catalyst 13 does not lead to any noticeable reopening of the cyclic olefin 12 once it is formed, although RCM is a priori a reversible transformation.…”

Polyesters ofω-Unsaturated Fatty Acid Derivatives

“…Polydispersities (M w /M n ) were 1.8-2.3, which are characteristic values obtained by (ADMET) polycondensations. [18] Generally, the real average molecular weights tended to be lower because of the low molecular weight fractions, which were not proportionately detected by the MALLS detector, effecting a shift of the calculated M w values.…”

“…[18] The synthesis of unsaturated polyesters and polycarbonates was reported by Wagener and coworkers using homogeneous tungsten and molybdenum carbene complexes, socalled "Schrock carbenes". [19,20] Therefore, we performed a screening of several homogeneous and heterogeneous metathesis catalysts capable of inducing ADMET polymerization of a,x-unsaturated esters using 1,4-bis(methylene)cyclohexylene diundecenoate II d as a standard monomer (see Scheme 3).…”

Undecylenic Acid: A Valuable and Physiologically Active Renewable Building Block from Castor Oil

“…[97,98,99 ] ADMET polymerization of a, walkylene dialkenoates 91 prepared from UA by acidic transesterification towards unsaturated polyesters was intensively studied. [59,60] ADMET polymerization of allyl 10-undecenoate 92 with Grubbs I catalyst resulted in a polymer 93 with a degree of polymerization (DP) varying between 41 and 79 (Scheme 23). Surprisingly, this did not work for other aliphatic allyl esters, where only oligomers were obtained.…”

“…[58] A reverse strategy, which first transesterifies UA with diols and subsequently polymerizes the resulting a,w-alkylene dialkenoates via acyclic diene metathesis (ADMET), was elaborated. [59,60] Cross-metathesis of UA 1 and its methyl ester 2 with an excess of acrylonitrile towards the bifunctional nitrile acid 67 or nitrile ester 68, respectively, was successfully executed with Hoveyda catalyst II and subsequent in situ hydrogenation. These nitrile acids/esters are potential precursors for renewable polyamide formation (Scheme 13).…”