Stereoselective Construction of (E,Z)‐1,3‐Dienes and Its Application in Natural Product Synthesis

Abstract

The E,Z-configured 1,3-diene unit is a common motif in numerous bioactive natural products. Although several powerful methods are available to produce these motifs with high levels of selectivity, their construction within a complex, polyfunctionalised structure, such as a natural product, requires well-defined strategies to avoid undesirable reactions and low-to-moderate selectivities. The aim of this review is to provide a full account of the stereoselective strategies for building E,Z-configured 1,3-dienes, as well as to highlight selected total syntheses that employ them. 2.3. Heck Reactions 2.4. CÀ H activation reactions 2.5. Ir-Catalysed Olefinations 2.6. Carbonyl Olefination Reactions 2.7. Elimination Strategies 2.8. Double Bond Isomerisation Strategies 2.9. Metathesis Strategies 2.10. Ene-Yne Triple Bond Reduction Strategies 2.11. Organocatalysed 1,6-Michael Additions 3. Applications in Total Synthesis: Selected Examples 4. Conclusion

A Dual CuH- and Pd-Catalyzed Stereoselective Synthesis of Highly Substituted 1,3-Dienes

“…8,16 Olefination of carbonyl compounds with stoichiometric allyl nucleophiles has been widely employed in the synthesis of conjugated dienes, [19][20][21][22][23][24][25][26] however, the products are generally obtained as inseparable E/Z-mixtures (Figure 1A). [26][27] Although considerable advances have been made towards stereoselective olefination of carbonyl substrates, most methods to access 1,3-dienes result in the E,E-isomer. 18,24,26,28 To avoid the formation of isomeric product mixtures, transition-metal catalyzed cross-coupling utilizing preformed organometallic reagents and vinyl (pseudo)halides has emerged as a practical route to stereoselectively synthesize dienes (Figure 1B).…”

Modern Synthetic Methods for the Stereoselective Construction of 1,3-Dienes

“…Notwithstanding this synthetic interest, no comprehensive reviews dealing with the synthesis of 1,3-dienes have appeared in the past few years and the most recent one just covers the period 2005–2010 [ 41 ]. A review on the synthesis of 1,3-dienes has been published recently, but is restricted to the synthesis of ( E,Z )-1,3-dienes and its application in natural product synthesis [ 42 ].…”

Copper(I)-Catalyzed Regioselective Asymmetric Addition of 1,4-Pentadiene to Ketones

“…Isomerically pure 1,3-dienes are prevalent structural motifs in natural products. , For example, ( Z , E )-1,3-diene is present in macrolactin A, callystatin A, chivosazole F, and lactimidomycin. Moreover, 1,3-dienes are a class of synthetically versatile compounds in organic chemistry, which are easily converted into highly functionalized molecules via diversified strategies based on transition metal catalysis or photoredox catalysis. − The reductive coupling between 1,3-dienes and carbonyl compounds or imines is particularly appealing, which affords synthetically useful homoallylic alcohols or amines .…”