Preparation of Enantiomerically Pure 5‐Palladatricyclo[4.1.0.0<sup>2, 4</sup>]heptanes and Conversion into Enantiomerically Pure Complexes with Helical Chirality at Palladium

Hashmi, A. Stephen K.; Naumann, Frank; Probst, Ralf; Bats, Jan W.

doi:10.1002/anie.199701041

Cited by 26 publications

(6 citation statements)

References 44 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The latter, upon treatment with (+)-DIOP, were converted to separable diastereomeric complexes 231 and 232 (Scheme 77). 151 An alternative approach to optically active palladacycles involved metallacyclization of cyclopropene 233 bearing two (S)-lactate auxiliaries. C 2 -symmetric compound 234 was obtained as a major product in a mixture with small amounts of other diastereomers (Scheme 78).…”

Section: Metallacyclization Reactionsmentioning

confidence: 99%

Transition Metal Chemistry of Cyclopropenes and Cyclopropanes

2007

View full text Add to dashboard Cite

Section: Metallacyclization Reactionsmentioning

confidence: 99%

Transition Metal Chemistry of Cyclopropenes and Cyclopropanes

2007

View full text Add to dashboard Cite

“…[19] Some years later, Hashmi and co-workers extended this approach to the use of 1,2-dicarboxyalkyl-3,3-dimethylcyclopropenes (Scheme 14). [20] In this case the reaction afforded the coordination polymer 20, similarly to what happened in the case of the palladols produced with DMAD (Scheme 6). The addition of a suitable ligand afforded the corresponding mononuclear species 21.…”

Section: Synthesis Involving Oxidative Cycloadditionmentioning

confidence: 61%

Chasing C,C‐Palladacycles

Garcı́a-López

Saura‐Llamas

2021

Eur J Inorg Chem

View full text Add to dashboard Cite

The different approaches for the synthesis of C,C-palladacycles are reviewed in this manuscript. These species hold a bidentate ligand that chelates the Pd atom through two C-donor moieties. Their relevance is closely related to the fact that they are intermediates in many palladium-catalyzed transformations. Furthermore, some of them have been used as efficient catalyst in cross coupling reactions. The review is structured according to the different strategies that have been employed to achieve the synthesis of the C,C-palladacycle derivatives, starting with those involving one elemental step (such as the oxidative addition of strained CÀ C bonds to Pd(0) or the transmetalation reactions between organometallic reagents and Pd(II) precursors), and continuing with more complex processes, where at least two elementary steps of Pd chemistry are involved (for example, carbometalation of alkenes followed by a CÀ H activation process). A final section highlights some aspects of synthetic methodologies based on Pd catalysis in which one or several C,C-palladacyclic intermediates are involved.Lenarda et al. synthesized the first reported four-membered C,C-palladacycles 1 a and 1 b in 1972, [5] via the oxidative addition of 1,1,2,2-tetracyanocyclopropane to [Pd(PPh 2 R) 4 ] (R = Ph; Me) (Scheme 1). The reaction occurred with the CÀ C bond cleavage of the highly strained ring and oxidative addition of the two resulting fragments to Pd(0).

show abstract

“…A major challenge was the synthesis of such compounds. We had previously succeeded both in a resolution of racemic 5‐pallada‐ trans ‐tricyclo[4.1.0.0 2,4 ]heptanes 1 1 and in a highly diastereoselective synthesis of enantiomerically pure 1 2…”

Section: Introductionmentioning

confidence: 99%

Different Diastereoselectivities in the Stereoselective Oxidative Cyclization of Two Cyclopropenes at Palladium(0)

et al. 2002

View full text Add to dashboard Cite

The C s -symmetrical cyclopropene 4a provided the palladacycle exo,exo-5 as the major product, accompanied by only small amounts of the endo,exo-5 isomer. The stereochemical assignments were accomplished by crystal structure analyses of the corresponding bpy, bis(acetone), and bis(acetonitrile) complexes. The enantiomerically pure, C 1 -symmetrical cyclopropene (S,S)-7, with two (S)-configured lactate units in the side-chain, delivered one dominant and three minor isomers. On the basis of one crystal structure analysis, the sym- [a]

show abstract

Preparation of Enantiomerically Pure 5‐Palladatricyclo[4.1.0.0^{2, 4}]heptanes and Conversion into Enantiomerically Pure Complexes with Helical Chirality at Palladium

Cited by 26 publications

References 44 publications

Transition Metal Chemistry of Cyclopropenes and Cyclopropanes

Transition Metal Chemistry of Cyclopropenes and Cyclopropanes

Chasing C,C‐Palladacycles

Different Diastereoselectivities in the Stereoselective Oxidative Cyclization of Two Cyclopropenes at Palladium(0)

Contact Info

Product

Resources

About

Preparation of Enantiomerically Pure 5‐Palladatricyclo[4.1.0.02, 4]heptanes and Conversion into Enantiomerically Pure Complexes with Helical Chirality at Palladium

Cited by 26 publications

References 44 publications

Transition Metal Chemistry of Cyclopropenes and Cyclopropanes

Transition Metal Chemistry of Cyclopropenes and Cyclopropanes

Chasing C,C‐Palladacycles

Different Diastereoselectivities in the Stereoselective Oxidative Cyclization of Two Cyclopropenes at Palladium(0)

Contact Info

Product

Resources

About

Preparation of Enantiomerically Pure 5‐Palladatricyclo[4.1.0.0^{2, 4}]heptanes and Conversion into Enantiomerically Pure Complexes with Helical Chirality at Palladium