Asymmetric Catalysis of the [5 + 2] Cycloaddition Reaction of Vinylcyclopropanes and π-Systems

Wender, Paul A.; Haustedt, Lars Ole; Lim, Joseph J.; Love, Jennifer A.; Williams, Travis J.; Yoon, Joo-Yong

doi:10.1021/ja058590u

Cited by 178 publications

(58 citation statements)

References 14 publications

(8 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In contrast to the vast number of precedents involving Rh-catalyzed [4 + 3]-cycloaddition reactions to form 7-membered-rings in a stereocontrolled manner [48–49], the use of the analogous gold-catalyzed transformations has remained, until recently, largely unexplored. Usually, 1, n -dipoles are elusive intermediate species, which can undergo many side reactions preceding the desired annulation/cyclization processes.…”

Section: Reviewmentioning

confidence: 99%

Synthetic applications of gold-catalyzed ring expansions

Garayalde

Nevado

2011

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

show abstract

Section: Reviewmentioning

confidence: 99%

Synthetic applications of gold-catalyzed ring expansions

Garayalde

Nevado

2011

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…[8][9][10] Furthermore,t he cyclization of 3c having a tert-butylsulfinyl imine under the same conditionsa fforded the cyclic compound 4c in 69% yield.…”

mentioning

confidence: 99%

Rhodium(I)‐Catalyzed [2+2+2] Cycloaddition between Allene, Alkyne, and Imine via a Strained Azarhodacycle Intermediate

2015

View full text Add to dashboard Cite

Ther hodium(I)-catalyzed intramolecular [2+ +2+ +2] cycloaddition between allenes,a lkynes, and imines has been developed. This cyclization proceeds via as trained azarhodacycle,g iving a5 ,7-fused cyclic amide or at ricyclic product containing an 8-azabicyclo[3.2.1]octane skeleton in high yield.Keywords: alkynes;a llenes;[ 2 + +2+ +2] cycloaddition; imines;rhodium Tr ansition metal-catalyzed [2+ +2+ +2] cycloadditions involving carbon-heteroatomm ultiple bonds as ac omponents hould be one of most straightforward strategies for the synthesiso fc omplicated heterocycles in ao ne-pot procedure.[1] There are aplethora of reports on transitionm etal-catalyzed [2+ +2+ +2] cycloadditions of two C-Cm ultiple bonds with aC Nt riple bond such as an itrilet oa fford pyridine or dihydropyridyne derivatives [Scheme 1, Eq. (1)].[1] On the other hand, [2+ +2+ +2] cycloadditions in which the C=Nd ouble bonds such as imines [2,3] or oximes [4] were employed remain rare [Scheme 1, Eq. (2) Initially,[ 2 + +2+ +2] cycloaddition using various C=N doubleb onds was tested (Scheme 3). Ther eactiono f allene-yne 3a having an oxime moiety in at ether under the optimal conditions previously reported by us {i.e., 10 mol% [Rh(dpbbz)]ClO 4 ,d ichloroethane, 80 8 8C} [5] did not afford the desired bicyclic compound 4a at all but produced 5-membered cyclicc ompounds 6a and 7a in 74% and 3% yields, respectively.T he compound 6a would be produced through oxidative cycloaddition of the allene and alkyne moieties to the Rh(I)c omplexf ollowed by b-hydridee limination from Ib and reductive elimination, while 7a was formed from 6a through elimination of the benzyl alcohol.[7] Ther esult suggestst hat the C=Nd ouble bond of the oxime could not be inserted into the C À Rh bond of rhodacycle intermediate Ib.W hen the substrate 3b having a p-toluenesulfinyl imine was tested in the reaction, the desired [2+ +2+ +2] product 4b was obtained in 33% yield as an almost1 :1 diastereomixture andthe yield of 5-membered ring 7b was suppressedt o2 %. [8][9][10] Furthermore,t he cyclization of 3c having a tert-butylsulfinyl imine under the same conditionsa fforded the cyclic compound 4c in 69% yield.[11] These results indicate that the nature of aC = Nd oubleb ondg reatly influencest he reactivity toward [2+ +2+ +2] cycloaddition.Next, the cyclization of 3c using various ligands was investigated, and the results are summarized in Table 1. Thec ycloaddition using dppe proceeded smoothly, giving the desired cyclic compound 4c in 59% yield (entry 2). When dpppw as employed in this Scheme 1. Cycloaddition involving C-N multiple bonds.

show abstract

“…98 The Hiyashi Group has more recently also reported a highly effective chiral phosphoramidite catalyst for this process. 99 We and others have also reported other catalysts that effect [5+2] cycloadditions between VCPs and pi-systems, including cationic rhodium, 100 rhodium NHC, 101 nickel, 102 ruthenium, 103 and iron 104 systems.…”

mentioning

confidence: 99%