Highly Enantio‐ and Diastereoselective Construction of 1,2‐Disubstituted Cyclopentane Compounds by Dirhodium(II) Tetrakis[N‐phthaloyl‐(S)‐tert‐leucinate]‐Catalyzed CH Insertion Reactions of α‐Diazo Esters

Minami, Kenji; Saito, Hiroaki; Tsutsui, Hideyuki; Nambu, Hisanori; Anada, Masahiro; Hashimoto, Shunichi

doi:10.1002/adsc.200505201

Cited by 89 publications

(22 citation statements)

References 51 publications

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“…Accordingly, a great deal of effort has been devoted to render the stereoselective synthesis of substituted cyclopropanes more appealing to organic chemists. [34][35][36][37][38][39][40] This has been further developed by the same group and others to include many other analogs. 31 Efforts in this area have led to the development of a family of dirhodium(II) carboxylate complexes that are derived from N-protected amino acids (Fig.…”

Section: Introductionmentioning

confidence: 99%

Rh₂(S‐1,2‐NTTL)₄: A Novel Rh₂(S‐PTTL)₄ Analog With Lower Ligand Symmetry for Asymmetric Synthesis of Chiral Cyclopropylphosphonates

2014

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A new series of dirhodium(II) tetracarboxylate was derived from N-1,2-naphthaloyl-(S)-amino acid ligands. In terms of enantioselectivity, Rh2 (S-1,2-NTTL)4 () derived from N-1,2-naphthaloyl-(S)-tert-leucine, was the best-performing catalyst among the new series in the enantioselective synthesis of cyclopropylphosphonate derivatives (up to >99% enantiomeric excess). A predictive model was proposed to justify the observed high enantiomeric induction exhibited by Rh2 (S-1,2-NTTL)4 with donor-acceptor phosphonate carbenoids.

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Section: Introductionmentioning

confidence: 99%

Rh₂(S‐1,2‐NTTL)₄: A Novel Rh₂(S‐PTTL)₄ Analog With Lower Ligand Symmetry for Asymmetric Synthesis of Chiral Cyclopropylphosphonates

2014

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“…[13][14][15] Herein, we report that [Rh 2 (S-tbpttl) 4 ] (1 f), a new dirhodium(II) carboxylate complex that incorporates N-tetrabromophthaloyl-(S)-tert-leucinate as chiral bridging ligands, catalyzes the cyclopropenation reaction of terminal alkynes with 2,4-dimethyl-3-pentyl a-alkyl-a-diazoacetates to give 1,2-disubstituted 2-cyclopropenecarboxylates in good to high yields and with up to 99 % ee. Scheme 1.…”

mentioning

confidence: 99%

Highly Enantioselective Cyclopropenation Reaction of 1‐Alkynes with α‐Alkyl‐α‐Diazoesters Catalyzed by Dirhodium(II) Carboxylates

Goto¹,

et al. 2011

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As a result of enormous ring strain, cyclopropene compounds display a range of diverse reactivities in both noncatalytic and transition-metal-catalyzed transformations, thus presenting unique opportunities for organic synthesis. [1,2] To further enhance the synthetic potential of cyclopropenes, the development of expeditious methods for the synthesis of enantioenriched cyclopropenes is highly desirable.[3] In this context, a cyclopropenation reaction of alkynes with diazo compounds that is catalyzed by chiral dirhodium(II) complexes represents one of the most powerful means for the construction of this class of optically active building blocks. Doyle, Müller, and co-workers were the first to demonstrate asymmetric induction (up to ! 98 % ee) in cyclopropenation reactions of terminal alkynes including propargyl alcohol or propargylamine derivatives with diazoacetates using [Rh 2 (5S-mepy) 4 ] (2 a; Scheme 1) as a chiral catalyst.[4] Doyle et al. also reported an enantioselective intramolecular cyclopropenation of diazoacetates, in which [Rh 2 (4S-ibaz) 4 ] (2 b) provided macrocyclic cyclopropenes in up to ! 99 % ee.[5] Corey and coworkers demonstrated that a new mixed carboxylate/carboxamidate catalyst [Rh 2 (OAc)(dpti) 3 ] (3) is highly exceptional for cyclopropenation of a broad range of terminal alkynes with ethyl diazoacetate.[6] The extension of this methodology to include a-substituted a-diazoacetates is particularly attractive because it has the capability to form cyclopropenes with a quaternary stereogenic carbon center. [7][8][9] Although high levels of enantioselectivity (up to 99 % ee) in cyclopropenations of terminal alkynes with aryldiazoacetates [7a] or arylvinyldiazoacetates [7b] under catalysis by [Rh 2 (S-dosp) 4 ] (4) have been reported by Davies and co-workers, the goal for the reaction with a-alkyl-a-diazoesters remains elusive because of the propensity to form a,b-unsaturated esters through a 1,2-hydride shift.[10] Panne and Fox recently disclosed that dirhodium(II) tetrapivalate exhibits high selectivity for cyclopropenation over alkene formation in the reaction of terminal alkynes with a-alkyl-a-diazoesters. [11,12] However, to the best of our knowledge, an enantioselective version of this reaction has not been reported.Our research group has previously demonstrated the first examples of highly enantio-, diastereo-, and chemoselective intramolecular C À H insertion reactions of a-alkyl-a-diazoesters by using dirhodium(II) tetrakis[N-phthaloyl-(S)-tertleucinate] ([Rh 2 (S-pttl) 4 ], 1 a) in which high levels of asymmetric induction (up to 95 % ee) were achieved. [13][14][15] Herein, we report that [Rh 2 (S-tbpttl) 4 ] (1 f), a new dirhodium(II) carboxylate complex that incorporates N-tetrabromophthaloyl-(S)-tert-leucinate as chiral bridging ligands, catalyzes the cyclopropenation reaction of terminal alkynes with 2,4-dimethyl-3-pentyl a-alkyl-a-diazoacetates to give 1,2-disubstituted 2-cyclopropenecarboxylates in good to high yields and with up to 99 % ee. Scheme 1. Chiral dirhodium(II) com...

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“…In 1993, Hashimoto, Ikegami and co-workers first reported their famous complex, Rh 2 (S-PTTL) 4 [76,77], as a catalyst that manifested (along with its variants) high enantioselectivity levels in wide range of organic transformations [2,54,[78][79][80][81][82][83][84]. For example, in enantioselective [2,3]-sigmatropic rearrangement of the cyclic propargylic oxonium ylide shown in Scheme 5a, Rh 2 (S-PTTL) 4 provided the best enantioselectivity of 79% ee of the corresponding allenic bearing benzofuran-3-one product (Scheme 5a) [85].…”

Section: Global Catalyst Symmetrymentioning

confidence: 99%

“…This assumption was based on the X-ray crystal structure of its analogue, Rh 2 (S-PTPA) 4 , which also showed moderate to good enantioselectivity in some asymmetric transformations [76,79,85,86]. For example, in aromatic C-H insertion of α-diazoketones, Rh 2 (S-PTPA) 4 resulted into the formation of the corresponding 1-alkyl-1-phenyl-2-indanones in up to 95% ee (Scheme 5b) [86].…”

Section: Global Catalyst Symmetrymentioning

confidence: 99%

On the Structure of Chiral Dirhodium(II) Carboxylate Catalysts: Stereoselectivity Relevance and Insights

Adly

2017

Catalysts

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Abstract:Modern experiments have offered alternative interpretations on the symmetry of chiral dirhodium(II) carboxylate complexes and its relationship to their level of enantioselectivity. So, this contribution is to provide an insight on how the knowledge around the structure of these catalysts has evolved with a particular emphasis on the impact of this knowledge on enantioselectivity prediction and catalyst design.

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Highly Enantio‐ and Diastereoselective Construction of 1,2‐Disubstituted Cyclopentane Compounds by Dirhodium(II) Tetrakis[N‐phthaloyl‐(S)‐tert‐leucinate]‐Catalyzed CH Insertion Reactions of α‐Diazo Esters

Cited by 89 publications

References 51 publications

Rh₂(S‐1,2‐NTTL)₄: A Novel Rh₂(S‐PTTL)₄ Analog With Lower Ligand Symmetry for Asymmetric Synthesis of Chiral Cyclopropylphosphonates

Rh₂(S‐1,2‐NTTL)₄: A Novel Rh₂(S‐PTTL)₄ Analog With Lower Ligand Symmetry for Asymmetric Synthesis of Chiral Cyclopropylphosphonates

Highly Enantioselective Cyclopropenation Reaction of 1‐Alkynes with α‐Alkyl‐α‐Diazoesters Catalyzed by Dirhodium(II) Carboxylates

On the Structure of Chiral Dirhodium(II) Carboxylate Catalysts: Stereoselectivity Relevance and Insights

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Highly Enantio‐ and Diastereoselective Construction of 1,2‐Disubstituted Cyclopentane Compounds by Dirhodium(II) Tetrakis[N‐phthaloyl‐(S)‐tert‐leucinate]‐Catalyzed CH Insertion Reactions of α‐Diazo Esters

Cited by 89 publications

References 51 publications

Rh2(S‐1,2‐NTTL)4: A Novel Rh2(S‐PTTL)4 Analog With Lower Ligand Symmetry for Asymmetric Synthesis of Chiral Cyclopropylphosphonates

Rh2(S‐1,2‐NTTL)4: A Novel Rh2(S‐PTTL)4 Analog With Lower Ligand Symmetry for Asymmetric Synthesis of Chiral Cyclopropylphosphonates

Highly Enantioselective Cyclopropenation Reaction of 1‐Alkynes with α‐Alkyl‐α‐Diazoesters Catalyzed by Dirhodium(II) Carboxylates

On the Structure of Chiral Dirhodium(II) Carboxylate Catalysts: Stereoselectivity Relevance and Insights

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Rh₂(S‐1,2‐NTTL)₄: A Novel Rh₂(S‐PTTL)₄ Analog With Lower Ligand Symmetry for Asymmetric Synthesis of Chiral Cyclopropylphosphonates

Rh₂(S‐1,2‐NTTL)₄: A Novel Rh₂(S‐PTTL)₄ Analog With Lower Ligand Symmetry for Asymmetric Synthesis of Chiral Cyclopropylphosphonates