Silyl-substituted 1,3-butadienes for Diels–Alder reaction, ene reaction and allylation reaction

Abstract

Silyl-substituted 1,3-butadienes are useful building blocks and are readily applied in several types of reactions such as Diels-Alder reaction, ene reaction and allylation. They can also participate in different tandem reactions such as Diels-Alder/allylation, ene/allylation, ene/allylation/Diels-Alder reaction, ene/allylation/ene reaction and ene/allylation/Diels-Alder/allylation reaction. This feature article reviews the synthesis of silyl-substituted 1,3-butadienes, and their applications in the reaction types mentioned above, involving a tandem Diels-Alder/ene/allylation process. This article also introduces some reactions of alkenylsilanes and allylsilanes for comparison and discussion about the tandem reaction. The tandem reactions described in this article are a powerful tool to construct complicated multicyclic compounds with high selectivity and high efficiency.

Boron and Silicon-Substituted 1,3-Dienes and Dienophiles and Their Use in Diels-Alder Reactions

“…This same ring system was formed via thermal reactions of pentaphenyl borole with cis diazenes so the authors proposed that photochemical trans - cis isomerization of the trans diazenes prior to cyclization accounted for the observed products. Formation of these 1,3,2-diazaborepins ( 51 ) ( Scheme 15 ) was thought to originate from an initial Diels-Alder reaction ( 52 ) followed by N-N bond heterolysis via a [ 1 , 3 ] sigmatropic shift. Coordination of the imine nitrogen thus liberated ( 53 ) to boron was proposed to set off a ring expansion that led to the observed product ( 54 ).…”

“…Reviews on boron diene/Diels-Alder chemistry were published in 2017 [ 1 ] and 2014 [ 2 ] so this review will cover that topic from 2016–2020. Silyl-substituted 1,3-dienes and their Diels-Alder reactions were reviewed in early 2011 [ 3 ] so this review will cover that chemistry from 2010–2020. The articles reviewed here came from one of four topical searches within the Science Citation Index.…”

Soybean-Based Polyols and Silanols

“…The first such example with a Lewis-acid promoted carbonyl-Ene reaction using vinylsilane as the ene moiety was published in 1990 (53). A recent comprehensive review of 'Ene' and Diels-Alder reactions involving vinyl and allylsilanes with emphasis on silyl-substituted 1,3-butadienes building blocks in organic synthesis is available (54).…”

Ultrasonic synthesis and crystal structure analysis of two trimethylsilyloxy-substituted bicyclo[2.2.2]octene derivatives

“…The atomic radius of silicon is larger than carbon, whereas the electronegativity of silicon is lower in comparison to carbon. 1 However, when elemental silicon is converted into organosilyl-based reagents, the silyl-groups behave as weak electron donating groups, becoming prone to attack by nucleophiles. 2 This renders the organosilyl-moiety to behave as anionic synthons.…”