1,4‐Diiodo‐1,3‐dienes: Versatile Reagents in Organic Synthesis

Abstract

1,4-Diiodo-1,3-dienes are unique reagents in organic synthesis and have been employed in several well-known and recently developed areas of application. Furthermore, these dienes are easily accessible, starting from the alkynes and iodine, and they have demonstrated high reactivity in cross-coupling reactions, organometallic synthesis, in the preparation of heterocyclic compounds, and several other transformations. The high reactivity of the 1,4-diiodo-1,3-dienes allows for the development of synthetic procedures that use mild conditions (room temperature). The key advantages in assembling complex organic molecules, natural products, and compounds for material science using 1,4-diiodo-1,3-dienes as building blocks include high yields, excellent selectivity, and diverse reactivity in carbon-carbon and carbon-heteroatom bond formation. This Focus Review describes the scope and application of the 1,4-diiodo-1,3-dienes in organic synthesis as well as summarizes the methods for preparation of the dienes.

Cooperative Iodide Pd(0)‐Catalysed Coupling of Alkoxyallenes and N‐Tosylhydrazones: A Selective Synthesis of Conjugated and Skipped Dienes

“…Another effective method is the functionalisation of 1,3‐dienes catalysed by Co or Pd . In the same way, the stereo‐defined construction of functionalised conjugated dienes represents a major goal in organic synthesis, and many efforts have been devoted in the past decades exploiting metal‐catalysed couplings of alkynes or allenes and suitable alkenes or 1,4 elimination processes . Nevertheless, great attention is still paid to their preparation –.…”

Visible Light Mediated Photocatalytic N-Radical Cascade Reactivity of γ,δ-Unsaturated N-Arylsulfonylhydrazones: A General Approach to Structurally Diverse Tetrahydropyridazines

“…49 1, dienes are ubiquitous structural units in natural products such as polyenic macrolides, [52][53][54] macrolactames, 55 and alkaloids 56 and also in functional materials. [57][58][59] Their synthesis is not trivial and in the last years the dearomatization approach has emerged as a powerful strategy to access this motif. 60 Optimization of reaction conditions for 10a is reported in Table 1.…”

Highly Selective Catalytic Synthesis of (E,E)-1,4-Diiodobuta-1,3-diene via Atom-Efficient Addition of Acetylene and Iodine: A Versatile (E,E)-1,3-Diene Building Block in Cross-Coupling Reactions

“…5,6 Synthesis of substituted diiododienes is a well-developed area, however, preparation of unsubstituted derivatives is a challenging problem. 5,6 Synthetic routes developed for substituted alkynes are generally not suitable for acetylene, and preparation of each C 4 H 4 I 2 compound requires a special procedure to be designed.…”

“…Diiododienes were established as an excellent building block for incorporation of 1,3-diene unit into complex organic molecules and for assembly of different types of lin-ear and cyclic structures around the 1,3-diene core. 5,6 Synthesis of substituted diiododienes is a well-developed area, however, preparation of unsubstituted derivatives is a challenging problem. 5,6 Synthetic routes developed for substituted alkynes are generally not suitable for acetylene, and preparation of each C 4 H 4 I 2 compound requires a special procedure to be designed.…”

“…5,6 Synthesis of substituted diiododienes is a well-developed area, however, preparation of unsubstituted derivatives is a challenging problem. 5,6 Synthetic routes developed for substituted alkynes are generally not suitable for acetylene, and preparation of each C 4 H 4 I 2 compound requires a special procedure to be designed. Moreover, highly reactive nature of these derivatives is reflected by many side reactions, which can take place even in the absence of metal catalysts (free-radical reactions, dimerization, photochemical transformations, polymerization, deiodination, etc.).…”