Chiral Supramolecular U-Shaped Catalysts Induce the Multiselective Diels–Alder Reaction of Propargyl Aldehyde

Abstract

The Diels–Alder reaction, which is a traditional [4 + 2] cycloaddition with two carbon–carbon bond formations, is one of the most powerful tools to synthesize versatile and unique six-membered rings. We show that chiral supramolecular U-shaped boron Lewis acid catalysts promote the unprecedented multiselective Diels–Alder reaction of propargyl aldehyde with cyclic dienes. Independent from the substrate control, enantio-, endo/exo-, π-facial-, regio-, site-, and substrate-selectivities could be controlled by the present U-shaped catalysts. The obtained reaction products could access the concise synthesis of chiral diene ligands and a key intermediate of (+)-sarkomycin. The results presented here might partially contribute to the development of artificial enzyme-like supramolecular catalysts for multiselective reactions, which will be able to target organic compounds that have thus far eluded synthesis.

Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold

“…10,11,12 In turn, the weak intermolecular interactions that govern supramolecular assemblies offer the undeniable advantage of easy functionalization, reversibility, and fast self-assembly 5,13,14 that overcome limitations of a delicate and more difficult redesign of an enzyme scaffold 15 . Supramolecular catalysts have the potential to revolutionize the chemical industry by allowing simpler and more flexible reaction pathways that offers lower cost, reduces the creation of undesired byproducts 16,17,18,19 , operates in a broad range of conditions. 20,21 , and is compatible with renewable and sustainable man-made chemistry.…”

Synthesis and photoswitching properties of bioinspired dissymmetric gamma-pyrone, analogue of cyclocurcumin

“…28,29 Unfortunately, in addition to partial polymerization (described as inevitable in the literature), the aldehyde 6 got oxidized into the corresponding carboxylic acid, and thus despite our various precautions (low temperature, dry and free oxygen conditions). 30 Thus, this strategy was not suitable for further developments.…”

B(C6F5)3‐Catalyzed α‐Deuteration of Bioactive Carbonyl Compounds with D2O

“…[6][7][8] We began by contemplating a method for αdeuteration of bioactive carbonyl compounds (1) by utilizing a Lewis acidic organoborane that can activate 1 towards deprotonation by D 2 O (Scheme 1C; I to II). [11][12][13][14] The application of frustrated Lewis pairs (FLPs), consisting of strongly Lewis acidic and hindered B(C 6 F 5 ) 3 and various Lewis bases, has emerged as an attractive strategy for overcoming undesired acid-base complexation. [11][12][13][14] The application of frustrated Lewis pairs (FLPs), consisting of strongly Lewis acidic and hindered B(C 6 F 5 ) 3 and various Lewis bases, has emerged as an attractive strategy for overcoming undesired acid-base complexation.…”

“…[9][10] A potential complication of this approach is that the Lewis acid may form stable acid-base adducts with D 2 O as well as Lewis basic functional groups that may be contained in 1. [11][12][13][14] The application of frustrated Lewis pairs (FLPs), consisting of strongly Lewis acidic and hindered B(C 6 F 5 ) 3 and various Lewis bases, has emerged as an attractive strategy for overcoming undesired acid-base complexation. [9,[12][13][14] We envisioned that B(C 6 F 5 ) 3 could activate 1, [9] thereby facilitating deprotonation by D 2 O to generate a boronenolate and D 2 O + À H (I to II).…”

“…[11][12][13][14] The application of frustrated Lewis pairs (FLPs), consisting of strongly Lewis acidic and hindered B(C 6 F 5 ) 3 and various Lewis bases, has emerged as an attractive strategy for overcoming undesired acid-base complexation. [9,[12][13][14] We envisioned that B(C 6 F 5 ) 3 could activate 1, [9] thereby facilitating deprotonation by D 2 O to generate a boronenolate and D 2 O + À H (I to II). [11][12] Ensuing deuteration of the enolate by D 2 O + À H would afford desired product 2.…”