Highly Enantioselective Synthesis of Multifunctionalized Dihydrofurans by Copper-Catalyzed Asymmetric [4 + 1] Cycloadditions of α-Benzylidene-β-ketoester with Diazo Compound

Zhou, Jiao‐Long; Wang, Lijia; Xu, Hao; Sun, Xiu‐Li; Tang, Yong

doi:10.1021/cs400019u

Cited by 60 publications

(14 citation statements)

References 79 publications

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“…The second test was a diazo-based [4 + 1] cycloaddition (Figure b) . This reaction included 6 novel ligands with the majority of the structural variation of the ligand architecture occurring on the methylene bridge.…”

Section: Introductionmentioning

confidence: 97%

“…The second test was a diazo-based [4 + 1] cycloaddition (Figure 4b). 16 This reaction included 6 novel ligands with the majority of the structural variation of the ligand architecture occurring on the methylene bridge. This is an interesting scenario as all reactions featuring diazo-based substrates in the training set result in cyclopropane products.…”

Section: ■ Introductionmentioning

confidence: 99%

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Linear Regression Model Development for Analysis of Asymmetric Copper-Bisoxazoline Catalysis

Werth

Sigman

2021

ACS Catal.

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Multivariate linear regression (MLR) analysis is used to unify and correlate different categories of asymmetric Cu-bisoxazoline (BOX) catalysis. The versatility of Cu-BOX complexes has been leveraged for several types of enantioselective transformations including cyclopropanation, Diels–Alder cycloadditions, and difunctionalization of alkenes. Statistical tools and extensive molecular featurization have guided the development of an inclusive linear regression model, providing a predictive platform and readily interpretable descriptors. Mechanism-specific categorization of curated data sets and parameterization of reaction components allow for simultaneous analysis of disparate organometallic intermediates such as carbenes and Lewis acid adducts, all unified by a common ligand scaffold and metal ion. Additionally, this workflow permitted the development of a complementary linear regression model correlating analogous BOX-catalyzed reactions employing Ni, Fe, Mg, and Pd complexes. Comparison of ligand parameters in each model reveals the relevant structural requirements necessary for high selectivity. Overall, this strategy highlights the utility of MLR analysis in exploring mechanistically driven correlations across a diverse chemical space in organometallic chemistry and presents an applicable workflow for related ligand classes.

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Section: Introductionmentioning

confidence: 97%

Section: ■ Introductionmentioning

confidence: 99%

Linear Regression Model Development for Analysis of Asymmetric Copper-Bisoxazoline Catalysis

Werth

Sigman

2021

ACS Catal.

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“…[9] Though, asymmetric version of some of these reactions have been reported, however, in most of the cases, five-membered heterocycle was obtained exclusively, rather than seven-membered heterocycles. [5], [10] Very recently, Schneider and coworkers reported a protocol for the construction of bicyclic framework: oxa-bridged dibenzooxacines (5-8 fused rings) via formal (4+3)-cycloaddition reaction involving carbonyl ylide as reactive intermediate. 11 Besides, the reaction of vinyl diazo compounds with aldehydes usually known to form a mixture of oxiranes [via (2+1)-cycloaddition] and dihydrofurans [via formal (3+2)-cycloaddition] through carbonyl ylide involving metal carbene intermediates (Scheme 1C).…”

Section: Introductionmentioning

confidence: 99%

A One-pot Access to Diastereoselective Benzo[5,6]oxepino[2,3-c]pyrroles via Formal (5+2)-Annulation of Donor-/Acceptor-Type Aryl Vinyl diazosuccinimide with Ketones Under Silver Catalysis

Bhat

Laha

Meher

et al. 2021

Preprint

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A silver triflimide catalyzed one-pot protocol for the diastereoselective synthesis of dihydrobenzoxepines has been developed. Silver triflimide found to be an efficient catalyst for the formal (5+2)-cycloaddition to access dihydrobenzoxepines as a single diastereomer using vinyl diazo compounds as 5-C-synthons and ketones. An unmet challenge of utilizing the donor-/acceptor-type vinyl diazosuccinimides as 5-C-synthons under silver-catalysis is presented. This protocol found to be highly regio-, chemo- and diastereoselective, and works well with aliphatic as well as aromatic methyl ketones bearing electron deactivating as well as donating groups to afford dihydrobenzo[5,6]oxepino[2,3-c]pyrroles with a broad substrates scope. The control experiments and time dependent NMR studies revealed the plausible mechanism of this transformation. The protocol also proved to be scalable on the gram scale synthesis.

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“…Moreover, a formal [6+1] addition reaction to yield dihydrobenzoxepines along with dihydrofurans was reported previously . Afterwards, copper‐catalyzed formal‐[4+1]/[5+1] cyclizations were widely investigated …”

Section: Introductionmentioning

confidence: 99%

Chemoselective Carbenoid Reactions of Furan/Thiophene/Pyrrole Ring Containing Carbonyl and Conjugated Carbonyl at Their 2‐Positions

2020

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Several furyl/thiophenyl/N‐methylpyrrolyl cores having aldehyde/ketone/ene‐biscarbonyl/diene‐biscarbonyl functions at their 2‐positions were reacted with diazocarbonyl compounds in the presence of metal catalysts. Between the two possible reaction pathways which may take place either on the 2‐substituent of hetaryl or on the core structure, only one of them was dominant for each reaction depending on substituents. Accordingly, in the reaction of thiophene‐2‐carbaldehyde with diazo compounds we obtained epoxy derivatives. On the other hand, dimethyl diazomalonate and furyl‐ene‐diketo/N‐methylpyrrolyl‐ene‐diester yielded only novel dihydrofuran derivatives via [1,5]‐electrocyclic ring closure. However, the reactions of 2‐ene/diene‐diester functionalized furans with dimethyl diazomalonate resulted polymethoxycarboxylate‐substituted oxo‐polyenes chemo‐specifically in good yields.

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Highly Enantioselective Synthesis of Multifunctionalized Dihydrofurans by Copper-Catalyzed Asymmetric [4 + 1] Cycloadditions of α-Benzylidene-β-ketoester with Diazo Compound

Cited by 60 publications

References 79 publications

Linear Regression Model Development for Analysis of Asymmetric Copper-Bisoxazoline Catalysis

Linear Regression Model Development for Analysis of Asymmetric Copper-Bisoxazoline Catalysis

A One-pot Access to Diastereoselective Benzo[5,6]oxepino[2,3-c]pyrroles via Formal (5+2)-Annulation of Donor-/Acceptor-Type Aryl Vinyl diazosuccinimide with Ketones Under Silver Catalysis

Chemoselective Carbenoid Reactions of Furan/Thiophene/Pyrrole Ring Containing Carbonyl and Conjugated Carbonyl at Their 2‐Positions

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