## 2 Applications in Chemistry
### Metal-Catalyzed Miscellaneous Reactions  
In recent years, the introduction of transition metal catalysis into diverse reactions has provided profitable results in organic chemistry. The most typical examples involve the use of palladium [67; 68; 69; 70; 71], platinum [72; 73; 74], rhodium [75; 76; 77], and magnesium [78] complexes. In addition, many studies have involved GC or vinylated carbonates as starting materials in coupling reactions to generate polymers and other important compounds. Targeting the synthesis of new glyceryl carbonate ethers through coupling reactions, [PERSON], [PERSON], and co-workers reported the telomerication between GC **1a** and 1,3-butadiene **26** (2 equivalent) in the presence of a catalytic system containing palladium bis(acetylacetonate), triphenylphosphine, and triethylamine as a base [79]. The reactions were performed over 17 h at temperatures ranging from \(-\)15 to 80 \({}^{\circ}\)C, giving the expected octadienylglycerol carbonate **1i** with 85% yield (Scheme 20, step 1). Compound **1i** was subsequently hydrogenated under Pd/C catalysis to the corresponding octyl ether **1j** (Scheme 20, step 2). The unsaturated glycerol carbonate ether **1i** was co-polymerized with \(\varepsilon\)-caprolactone **27** in the presence of a neodymium initiator [Nd(2,6-_tert_Bu2 OC6H3)3] to form the polymeric derivative **28** with 15-82% yields (Scheme 20, step 3). This polymer-bearing carbonate unit presents good thermomechanical properties. \begin{table}
\begin{tabular}{c c c c c} \hline \hline
**Entry** & **Condition** & **R** & **Product** & **Yield (\%)** \\ \hline \multirow{3}{*}{1} & \multicolumn{3}{c}{B\({}_{2}\)pin\({}_{2}\) **22** (1.2 equivalent)} & \multirow{3}{*}{aryl} & HO \\  & & CuCl (9 mol\%)/ & & \\  & **L1** (13 mol\%), Cs\({}_{2}\)CO\({}_{3}\) (15 mol\%), CH\({}_{3}\)OH, r.t., 16 & & & \\  & & h & & \\ \hline \multirow{3}{*}{2} & \multicolumn{3}{c}{Bpin(CH\({}_{2}\))Bpin **23**, (1.2 equivalent)} & \multirow{3}{*}{aryl, heteroaryl, vinyl} & HO \\  & & CuCl (9 mol\%), Cs\({}_{2}\)CO\({}_{3}\) (50 mol\%), CH\({}_{3}\)OH, r.t., 16 & & \\  & & & & \\ \hline \multirow{3}{*}{3} & \multicolumn{3}{c}{B\({}_{2}\)pin\({}_{2}\) **22** (1.2 equivalent)} & \multirow{3}{*}{alkyl, aryl, heteroaryl} & OH \\  & & CuCl (9 mol\%)/ & & \\  & **L2** (13 mol\%), Cs\({}_{2}\)CO\({}_{3}\) (15 mol\%), CH\({}_{3}\)OH, r.t., 16 & & & \\  & & h & & \\ \hline \multirow{3}{*}{4} & \multicolumn{3}{c}{Pd\({}_{2}\)(dba)\({}_{3}\)CHCl\({}_{3}\) (2.5 mol\%)} & \multirow{3}{*}{aryl, heteroaryl} & HO \\  & & &Several studies showing the efficiency of the palladium catalysis in the allylic cycloaddition of vinylated carbonates **6** have been published [80; 81; 82; 83; 84]. For example, [PERSON] and co-workers [80] demonstrated the interesting Pd-catalyzed decarboxylase heterocyclization of [60]fullerene for the preparation of novel vinyl-substituted [60]fullerene-fused tetrahydrorofurans, pyrans, or quinolines. In 2018, through a cooperative \(N\)-heterocyclic carbene (NHC) organocatalysis and palladium catalysis, [PERSON] and co-workers [81] performed enantioselective [5+2] annualations of canals **11** with vinylated carbonates **6** (VECs) for the synthesis of lactone **29**. The reaction was performed over 10-12 h at room temperature in toluene solution in the presence of a cooperative \(N\)-heterocyclic carbene (NHC)/Pd catalytic system, along with (\(R\))-Tol-BINAP **L1** as a ligand and \(N\)-methylpiperidine. A library of twenty-six examples was obtained with 30-99% yields and 92-99% _ee_ (Scheme 21). [PERSON], [PERSON], and co-workers [82] also used a Pd\({}_{2}\)(dba)\({}_{3}\)-containing system for the synthesis of nine-membered cyclic compounds **30**, starting from azadienes **31** and VECs **6**. In the presence of ligand **L2** (5 mol%), this formal [5+4] cycloaddition led to the enantioselective preparation of twenty-four new heterocyclic compounds **30** with 70-95% yields (80-92% _ee_) (Scheme 21).