Asymmetric Copper-Catalyzed Carbomagnesiation of Cyclopropenes

The highly diastereo- and enantioselective formation of polysubstituted cyclopropanes was easily achieved through the asymmetric copper-catalyzed carbomagnesiation reaction of nonfunctionalized cyclopropene derivatives. The carbometalated species generated in situ readily undergo C−C and C−X bond-forming reactions with various electrophiles with complete retention of configuration.     

Catalytic Synthesis of Trifluoromethyl Cyclopropenes and Oligo-Cyclopropenes

The synthesis of trifluoromethylated cyclopropenes is often associated with important applications in drug discovery and functional materials. In this report, we describe the use of readily available chiral rhodium(II) catalysts for a highly efficient asymmetric cyclopropenation reaction of fluorinated donor–acceptor diazoalkanes with a broad variety of aliphatic and aromatic alkynes. Further studies highlight the unique reactivity of fluorinated donor–acceptor diazoalkanes in the synthesis of oligo-cyclopropenes. Subsequent C−H functionalization of trifluoromethyl cyclopropenes furnishes densely substituted cyclopropene frameworks and also allows the alternative synthesis of bis-cyclopropenes.     

Copper-Catalyzed Enantio- and Diastereoselective Addition of Silicon Nucleophiles to 3,3-Disubstituted Cyclopropenes

A highly stereocontrolled syn-addition of silicon nucleophiles across cyclopropenes with two different geminal substituents at C3 is reported. Diastereomeric ratios are excellent throughout (d.r.≥98:2) and enantiomeric excesses usually higher than 90 %, even reaching 99 %. This copper-catalyzed C−Si bond formation closes the gap of the direct synthesis of α-chiral cyclopropylsilanes.     

Catalyst‐Controlled Ring‐Opening Cycloisomerization Reactions of Cyclopropenyl Carboxylates for Highly Regioselective Synthesis of Different 2‐Alkoxyfurans

Differently substituted 2‐alkoxyfurans (2,3,4‐ or 2,3,5‐trisubstituted furans) were highly regioselectively synthesized by means of the ring‐opening cycloisomerization of the same cyclopropenyl carboxylates with good yields in different solvents and excellent regioselectivity by using [Cu(acac)₂] (acac=acetylacetonate) or [RuCl₂(PPh₃)₃] as the catalyst, respectively. The structures of these two different types of furans were established by X‐ray diffraction studies. A rationale has been proposed.     

Rhodium‐Catalyzed Arylation of Cyclopropenes Based on Asymmetric Direct Functionalization of Three‐Membered Carbocycles

A variety of highly diastereo‐ and enantiomerically enriched arylcyclopropanes is obtained through the asymmetric rhodium‐catalyzed arylation reaction of achiral nonfunctionalized cyclopropene derivatives with commercially available aryl boronic acids in the presence of (R,S)‐Josiphos.     

Total Synthesis of C30 Botryococcene and epi‐Botryococcene by a Diastereoselective Ring Opening of Alkenylcyclopropanes

Trialkylaluminum compounds perform a diastereoselective 1,6‐ring fragmentation of alkenylcyclopropane. This new tool allows the preparation of hydrocarbon compounds containing two distant stereocenters with a good diastereocontrol. Inspired by the biosynthesis of botryococcene this methodology was applied successfully to the diastereo‐ and enantioselective preparation of this triterpene and its epimer.     

Diastereoselective alkylations of β-tetrazolyl propionic acids

A new procedure for the diastereoselective alkylations of β-tetrazolyl propionic acids is described. A seven-membered chelation model is proposed to rationalize the observed high level of syn selectivity.     

Efficient Synthesis of Arylated Furans by a Sequential Rh‐Catalyzed Arylation and Cycloisomerization of Cyclopropenes

A novel and efficient strategy for the synthesis of arylated furans was successfully developed by a Rh^III‐catalyzed coupling of N‐phenoxyacetamides and cyclopropenyl esters. Mechanistic investigation reveals that the arylated furans are formed via arylation of the cyclopropenyl esters followed by cycloisomerization.     

Taming the Carboxyl Group for Directed Carbometalation: Observations on the Use of Anions,Dianions and Ester Enolates

Carboxylate anions, dianions and ester enolates provide simultaneous protection and activation for directed carbometalation reactions. Advantage can be taken of the bis‐carbanionic character of the intermediate for further controlled C?C bond forming reactions.     

Highly Diastereoselective and Regioselective Copper‐Catalyzed Nitrosoformate Dearomatization Reaction under Aerobic‐Oxidation Conditions

An unprecedented copper‐catalyzed acylnitroso dearomatization reaction, which expands the traditional acylnitroso ene reaction and acylnitroso Diels–Alder reaction to a new type of transformation, has been developed under aerobic oxidation. Intermolecular and intra‐/intermolecular reaction modes demonstrate an entirely different N‐ or O‐acylnitroso selectivity. Hence, we can utilize this reaction as a highly diastereoselective access to a series of new pyrroloindoline derivatives, which are important structural motifs for natural‐product synthesis.     

First and Highly Diastereoselective Synthesis of Palladepanes

Unexpected stability is observed for the palladacycloheptane rac-2, which is obtained as major product and single diastereomer from the cyclization of 1 and Pd(0). Up to a temperature of 50 degrees C 2 shows neither reductive elimination nor intramolecular insertion of another olefin.     

Diastereoselective reductive aldol reactions of Boc-protected electron deficient pyrroles

An anti-selective reductive aldol reaction of a Boc-protected, 2-substituted pyrrole is reported. Reduction with LiDBB generates an exocyclic lithium enolate, but optimal stereoselectivity is obtained by transmetallation to magnesium with MgBr₂·OEt₂. The corresponding syn-aldols can easily be obtained (protected as carbamates) by subsequent inversion.     

Highly Diastereoselective Addition of Allyltitanocenes to Ketones

A route with less congestion : A practical method for the highly diastereoselective preparation of anti tertiary homoallylic alcohols has been developed. The reaction of allyltitanocenes, generated by the reductive titanation of various allylic substrates with a titanocene(II) species, with a variety of ketones produced the anti tertiary homoallylic alcohols in good diastereoselectivity, even when using sterically less congested ketones (see scheme; Cp: cyclopentadienyl; Piv: pivaloyl).

     

Diastereoselective Synthesis of Highly Functionalized Proline Derivatives

An efficient way to access highly functionalized proline derivatives was developed based on a Cu(I)-catalyzed reaction between CF₃-substituted allenynes and tosylazide, which involved a cascade of [3 + 2]-cycloaddition/ketenimine and a rearrangement/Alder-ene cyclization to afford the new proline framework with a high diastereoselectivity.     

Highly Diastereoselective Metal-Free Catalytic Synthesis of Drug-Like Spiroimidazolidinone

Russian Journal of Organic Chemistry - A four-step procedure has been developed for the synthesis of (S)-3-isopropyl-1-[(R)-1-phenylethyl)- 1,4-diazaspiro[4.5]decan-2-one with high...