Enantioselective Catalytic [4+1]-Cyclization of ortho-Hydroxy-para-Quinone Methides with Allenoates.

The first highly asymmetric catalytic synthesis of densely functionalized dihydrobenzofurans is reported, which starts from ortho-hydroxy-containing para-quinone methides. The reaction relies on an unprecedented formal [4+1]-annulation of these quinone methides with allenoates in the presence of a commercially available chiral phosphine catalyst. The chiral dihydrobenzofurans were obtained as single diastereomers in yields up to 90 % and with enantiomeric ratios up to 95:5.

Asymmetric phase-transfer catalysed ß-addition of isoxazolidin-5-ones to MBH carbonates.

A novel high yielding, enantio- and diastereoselective protocol for the synthesis of α-allylated highly functionalised ß-amino acid derivatives by adding isoxazolidin-5-ones to MBH carbonates under asymmetric phase-transfer catalysis has been developed.

Formal (4+1)-Cyclization of Ammonium Ylides with Vinylogous para-Quinone Methides.

The formal (4+1)-cyclization between in situ generated achiral carbonyl-stabilized ammonium ylides and vinylogous p-quinone methides can be carried out under operationally simple conditions, leading to two different double bond regioisomers depending on the used conditions. Besides these racemic approaches, also a first proof-of-concept for enantioselective versions of these reactions has been obtained.

Ammonium Ylide Mediated Cyclization Reactions.

The use of readily accessible ammonium ylides for (asymmetric) transformations, especially cyclization reactions, has received considerable attention over the past two decades. A variety of highly enantioselective protocols to facilitate annulation reactions have recently been introduced as an alternative to other common methods including S-ylide-mediated strategies. It is the intention of this short review to provide an introduction to this field by highlighting the potential of ammonium ylides for (asymmetric) cyclization reactions as well as to present the limitations and challenges of these methods.

Syntheses of Highly Functionalized Spirocyclohexenes by Formal [4+2] Annulation of Arylidene Azlactones with Allenoates.

A straightforward phosphine-catalyzed formal [4+2] annulation between α-branched allenoates and arylidene azlactones has been developed to access highly functionalized spirocyclohexenes. This cyclization favors the γ-addition of the phosphine-activated allenoates over a ß'-addition pathway. Detailed computational studies support the proposed mechanism and provide a reasonable explanation for the observed regioselectivity and the noted effect of the catalyst.

Synthesis of Trifluoroacetyl-Substituted Cyclopropanes Using Onium Ylides.

The use of carbonyl-stabilized ammonium- and sulfonium ylides allows for the synthesis of highly-functionalized trifluoroacetyl-substituted cyclopropanes. It turned out that the diastereoselectivities strongly depend on the nature of the chosen ylide and the employed base. The products could be obtained in good yields under operationally simple conditions.

Formal (4 + 1)-Addition of Allenoates to o-Quinone Methides.

The first (4 + 1)-annulation of o-quinone methides with α-branched allenoates as C1 synthons has been developed. This operationally simple protocol gives access to highly functionalized dihydrobenzofurans in an unprecedented fashion with excellent diastereoselectivities and high yields.

Towards a General Understanding of Carbonyl-Stabilised Ammonium Ylide-Mediated Epoxidation Reactions.

The key factors for carbonyl-stabilised ammonium ylide-mediated epoxidation reactions were systematically investigated by experimental and computational means and the hereby obtained energy profiles provide explanations for the observed experimental results. In addition, we were able to identify the first tertiary amine-based chiral auxiliary that allows for high enantioselectivities and high yields for such epoxidation reactions.