Rhodium-catalyzed enantio- and diastereoselective intramolecular [2 + 2 + 2] cycloaddition of unsymmetrical dienynes

Sagae, Hiromi; Noguchi, Keiichi; Hirano, Masao; Tanaka, Ken

doi:10.1039/b804294b

Cited by 38 publications

(14 citation statements)

References 27 publications

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“…Cationicr hodium(I)/(R)-H 8 -BINAP or (R)-SEGPHOS complexes wereu sed as the catalytic systems, achieving high yields and stereoselectivities (Scheme 21). [46] The reactions of dienynes (ene-ene-ynes) catalyzed by rhodium were reported by Shibata andc o-workers. They found that, depending on the substitution pattern,t he starting dienyne gave alternatively cyclohexadienes or strained polycyclic compounds.…”

Section: Scheme14 Asymmetric Cycloaddition Of Diynes With Norbornenementioning

confidence: 96%

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Alkenes in [2+2+2] Cycloadditions

Domı́nguez

Pérez‐Castells

2016

Chemistry A European J

127

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Participation of alkenes and allenes in [2+2+2] cycloaddition reactions has attracted much attention recently. This version of the well-established alkyne cyclotrimerization renders interesting products, such as cyclohexadienes and other polycycles, through cascade processes. Many mechanistic variations are observed when using certain metal complexes as catalysts. The frequent generation of stereogenic centers has prompted the development of efficient asymmetric versions. This Minireview summarizes the efforts reported to date on the use of double bonds as partners in [2+2+2] cyclotrimerizations.

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Section: Scheme14 Asymmetric Cycloaddition Of Diynes With Norbornenementioning

confidence: 96%

“…In addition to endiynes, dienynes (ene–yne–ene) allowed the synthesis of fused tricyclic cyclohexenes bearing two tertiary or quaternary carbon centers. Cationic rhodium(I)/( R )‐H 8 ‐BINAP or ( R )‐SEGPHOS complexes were used as the catalytic systems, achieving high yields and stereoselectivities (Scheme ) …”

Section: Rhodium and Iridium Catalysismentioning

confidence: 99%

Alkenes in [2+2+2] Cycloadditions

Domı́nguez

Pérez‐Castells

2016

Chemistry A European J

127

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“…[35] Under these mild conditions, strained polycyclic compounds containing pairs of quaternary centers can be formed with great efficiency (Scheme 15). [36] Judicious design of the corresponding substrates allows the straightforward formation of tricyclic or tetracyclic cyclohexene derivatives also incorporating tertiary or quaternary new stereocenters (Scheme 16). [36] Judicious design of the corresponding substrates allows the straightforward formation of tricyclic or tetracyclic cyclohexene derivatives also incorporating tertiary or quaternary new stereocenters (Scheme 16).…”

Section: Dienyne Cycloadditionsmentioning

confidence: 99%

Recent Advances in Stereoselective [2+2+2] Cycloadditions

2014

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The [2+2+2] cycloaddition reaction is considered one of the most efficient methods for the rapid and straightforward preparation of complex polycyclic (and heterocyclic) compounds in a highly selective and atom‐economical fashion. Over the last half‐century, remarkable advances in terms of chemo‐ and regioselectivities have been realized, endowing this reaction with attractive features as a key step in the synthesis of various biologically active molecules and materials. The development of stereoselective methodologies is more recent. In this field, asymmetric transition‐metal catalysis has emerged as the most convenient tool with which to perform these [2+2+2] cycloadditions in their enantio‐ and diastereoselective variants. All the catalytic systems that have been developed so far are based on very close association of a transition metal (Co, Ni, Ir, Rh, ...) with a chiral ligand. The success of these reactions is then related to the reaction pattern involved (inter‐ and intramolecular), implying an efficient substrate/active species interaction. Thus, judicious design both of chiral ligands and of unsaturated substrates is necessary. In light of these aspects, numerous stereoselective cycloadditions have been reported; these allow the construction in one‐step fashion of central, axial, planar, and helical chiralities. This review details the recent advances in this area, with specific attention to catalysts and reaction scope.

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“…[1] For this asymmetric transformation, cationic rhodium(I)/axially chiral biaryl bisphosphine complexes showh igh catalytic activity and selectivity. [2] For example, our research group reported that ac ationic rhodium(I)/H 8 -binap complex is capableo fc atalyzing the regio-, diastereo-,a nd enantioselective [2+ +2+ +2] cycloaddition of 1,6-enynes [3,4] with acrylamides [5] giving chiral bicyclic cyclohexenes,p ossessing two stereogenic centers (Scheme 1a). [6] Not only acrylamides but also enamides [5a, 7] and oxabenzonorborna-dienes [8] could be employed in the rhodium-catalyzed asymmetric[ 2 + +2+ +2] cycloadditionw ith 1,6-enynes.…”

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Rhodium‐Catalyzed Asymmetric [2+2+2] Cycloaddition of 1,6‐Enynes with Racemic Secondary Allylic Alcohols through Kinetic Resolution

Suzuki

Shibata

Tanaka

2020

Chemistry A European J

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It has been established that a cationic rhodium(I)/P‐phos complex catalyzes the asymmetric [2+2+2] cycloaddition of 1,6‐enynes with racemic secondary allylic alcohols to produce the corresponding chiral bicyclic cyclohexenes, possessing three stereogenic centers, as a single diastereomer with excellent ee values. Mechanistic experiments revealed that the present cycloaddition proceeds through the kinetic resolution of the racemic secondary allylic alcohols, in which one enantiomer preferentially reacts with the 1,6‐enyne.

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Rhodium-catalyzed enantio- and diastereoselective intramolecular [2 + 2 + 2] cycloaddition of unsymmetrical dienynes

Cited by 38 publications

References 27 publications

Alkenes in [2+2+2] Cycloadditions

Alkenes in [2+2+2] Cycloadditions

Recent Advances in Stereoselective [2+2+2] Cycloadditions

Rhodium‐Catalyzed Asymmetric [2+2+2] Cycloaddition of 1,6‐Enynes with Racemic Secondary Allylic Alcohols through Kinetic Resolution

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