Borylated Cyclopropanes as Spring-Loaded Entities: Access to Vicinal Tertiary and Quaternary Carbon Stereocenters in Acyclic Systems

Article Chemistry, Multidisciplinary

Iridium-Catalyzed Enantioselective C(sp3)-H Borylation of Aminocyclopropanes

Yongjia Shi et al.

Summary: This study presents the first example of transition-metal-catalyzed regio- and stereo-controllable C-H functionalization, achieving a broad range of functional groups and high enantioselectivities.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Organic

Simmons-Smith Cyclopropanation of Alkenyl 1,2-Bis(boronates):Stereoselective Access to Functionalized Cyclopropyl Derivatives

Maruti Mali et al.

Summary: A Simmons-Smith stereodefined procedure for the synthesis of cyclopropyl-1,2-bis(boronates) starting from alkenes has been developed. The resulting compounds were then subjected to regioselective Suzuki-Miyaura couplings to produce diversely substituted arylcyclopropanes in good yields.

JOURNAL OF ORGANIC CHEMISTRY (2022)

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Article Chemistry, Multidisciplinary

Ir-Catalyzed Asymmetric Allylic Alkylation of Dialkyl Malonates Enabling the Construction of Enantioenriched All-Carbon Quaternary Centers

Farbod A. Moghadam et al.

Summary: An enantioselective iridium-catalyzed allylic alkylation of malonates with trisubstituted allylic electrophiles to form all-carbon quaternary stereocenters is reported. This reaction proceeds at ambient temperature and enables the preparation of a wide range of enantioenriched products in up to 93% yield and 97% ee. The quaternary products can be readily converted to several valuable building blocks such as vicinal quaternary products and beta-quaternary acids.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

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Article Chemistry, Multidisciplinary

Stereospecific Construction of Quaternary Carbon Stereocenters from Quaternary Carbon Stereocenters

Kaushalendra Patel et al.

Summary: Organic aluminum species have been found to facilitate a smooth nucleophilic substitution reaction at a quaternary carbon stereocenter of a stereodefined polysubstituted cyclopropyl methyl phosphate, even in the presence of more reactive functional groups. The regio- and diastereoselectivity of the substitution reaction is attributed to the existence of a bicyclobutonium intermediate.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

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Article Chemistry, Organic

Asymmetric Synthesis of Tertiary and Secondary Cyclopropyl Boronates via Cyclopropanation of Enantioenriched Alkenyl Boronic Esters

Alvaro Gutierrez-Bonet et al.

Summary: In this study, we demonstrated the asymmetric cyclopropanation of enantioenriched hydrobenzoin-derived alkenyl boronic esters for the synthesis of tertiary and secondary cyclopropyl boronates. The cyclopropanation reaction, together with subsequent derivatization of the boronate handle, provides a convenient strategy to access diverse compounds with a high sp(3) fraction and quickly build molecular complexity.

ORGANIC LETTERS (2022)

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Article Chemistry, Organic

Synthetic Doping of Diamondoids through Skeletal Editing

Andrey A. Fokin et al.

Summary: This study presents a strategy for selectively replacing methylene with heteroatom moieties in diamondoid structures, allowing the doping of diamond-like structures with electron donor dopants. The approach involves retro-Barbier fragmentations and cage reconstruction, ultimately reducing the strain of the diamondoid cage.

ORGANIC LETTERS (2022)

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Article Chemistry, Organic

Synthesis of Cyclopropyl Pinacol Boronic Esters from Dibromo-cyclopropanes

Zeina Neouchy et al.

Summary: A method for synthesizing cyclopropyl pinacol boronic esters from di-bromocyclopropanes via Matteson-Pasto rearrangement is reported. The method is scalable and exhibits limited levels of stereoinduction, with a selectivity that complements existing stereoselective borylcyclopropanation strategies. It can be utilized to rapidly access interesting building blocks for diversely functionalized cyclopropanes.

SYNLETT (2022)

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Article Chemistry, Multidisciplinary

Conformationally Fixed Chiral Bisphosphine Ligands by Steric Modulators on the Ligand Backbone: Selective Synthesis of Strained 1,2-Disubstituted Chiral cis-Cyclopropanes

Hiroaki Iwamoto et al.

Summary: A new series of C-1-symmetric P-chirogenic bisphosphine ligands have been developed, which showed high performance in a copper(I)-catalyzed asymmetric borylation reaction. Computational studies highlighted the importance of the highly rigid phosphine conformation in achieving high stereo- and product-selectivities.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

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Review Chemistry, Multidisciplinary

Creating Stereocenters within Acyclic Systems by C-C Bond Cleavage of Cyclopropanes

Yair Cohen et al.

Summary: Recent advancements in the stereoselective synthesis of polysubstituted cyclopropanes have enabled chemists to access these strained rings with high diastereomeric and enantiomeric ratios. This development has led to a paradigm shift in the synthesis of stereodefined acyclic molecules through selective carbon-carbon bond cleavage. Application of these concepts has been demonstrated in the total syntheses of various natural products and important molecules, highlighting the power of these strategies in organic synthesis.

CHEMICAL REVIEWS (2021)

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Article Chemistry, Multidisciplinary

Stereoselective Synthesis of Cyclobutanes by Contraction of Pyrrolidines

Chunngai Hui et al.

Summary: This report presents a contractive synthesis of multisubstituted cyclobutanes from readily accessible pyrrolidines using iodonitrene chemistry. The stereospecific synthesis of cyclobutanes through a radical pathway mediated by a nitrogen extrusion process is described, resulting in the successful preparation of unprecedented unsymmetrical spirocyclobutanes, as well as a concise, formal synthesis of the cytotoxic natural product Piperarborenine B.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Construction of Vicinal Quaternary Centers via Iridium-Catalyzed Asymmetric Allenylic Alkylation of Racemic Tertiary Alcohols

Mayuko Isomura et al.

Summary: A robust catalytic system utilizing chiral Ir-phosphoramidite and La(OTf)(3) enables highly enantioselective alkylation reactions of racemic tertiary alpha-allenyl alcohols with tetrasubstituted silyl ketene acetals. The reaction displays broad functional group tolerance and allows efficient generation of beta-allenyl ester products with excellent enantioselectivity, which can be further upgraded in structural complexity via stereoselective metal-catalyzed functionalization reactions.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Regio- and Diastereoselective Copper-Catalyzed Carbomagnesiation for the Synthesis of Penta- and Hexa-Substituted Cyclopropanes

Yair Cohen et al.

Summary: The regio- and diastereoselective copper-catalyzed carbomagnesiation reaction of cyclopropenes provides an easy and efficient access to novel persubstituted cyclopropyl cores with complete regio- and diastereoselectivity, despite the highly strained nature of cyclopropanes possessing three vicinal quaternary carbon stereocenters.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Multidisciplinary Sciences

Skeletal editing through direct nitrogen deletion of secondary amines

Sean H. Kennedy et al.

Summary: This reaction successfully removes nitrogen from organic molecules, promoting carbon-carbon coupling reactions and expanding the accessible chemical space.

NATURE (2021)

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Article Chemistry, Multidisciplinary

Carbon Atom Insertion into Pyrroles and Indoles Promoted by Chlorodiazirines

Balu D. Dherange et al.

Summary: This study presents a reaction for selectively generating 3-arylpyridine and quinoline motifs by inserting aryl carbynyl cation equivalents into pyrrole and indole cores. The use of α-chlorodiazirines as thermal precursors allows for a modification of the traditional protocol to directly afford these compounds. Selectivity based on pyrrole substitution patterns is examined, with a predictive model proposed based on steric effects.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Review Chemistry, Multidisciplinary

Synthesis of Enantioenriched Vicinal Tertiary and Quaternary Carbon Stereogenic Centers within an Acyclic Chain

David Pierrot et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Article Chemistry, Multidisciplinary

Nucleophilic Substitution at Quaternary Carbon Stereocenters

Veeranjaneyulu Lanke et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

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Article Chemistry, Multidisciplinary

Copper-Catalyzed Synthesis of Stereodefined Cyclopropyl Bis(boronates) from Alkenes with CO as the C1 Source

Fu-Peng Wu et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

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Article Chemistry, Multidisciplinary

Difunctionalization of C-C σ-Bonds Enabled by the Reaction of Bicyclo[1.1.0]butyl Boronate Complexes with Electrophiles: Reaction Development, Scope, and Stereochemical Origins

Steven H. Bennett et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

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Article Chemistry, Organic

Scalable Synthesis of Vicinal Quaternary Stereocenters via the Solid-State Photodecarbonylation of a Crystalline Hexasubstituted Ketone

Trevor Y. Chang et al.

ORGANIC LETTERS (2020)

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Review Chemistry, Multidisciplinary

Stereospecific nucleophilic substitution at tertiary and quaternary stereocentres

Veeranjaneyulu Lanke et al.

CHEMICAL SCIENCE (2020)

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Article Chemistry, Organic

Strain Release of Donor-Acceptor Cyclopropyl Boronate Complexes

Charlotte H. U. Gregson et al.

ORGANIC LETTERS (2019)

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Article Chemistry, Multidisciplinary

Carbopalladation of C-C σ-bonds enabled by strained boronate complexes

Alexander Fawcett et al.

NATURE CHEMISTRY (2019)

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Review Multidisciplinary Sciences

The importance of synthetic chemistry in the pharmaceutical industry

Kevin R. Campos et al.

SCIENCE (2019)

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Article Chemistry, Multidisciplinary

Enantioselective Synthesis of Vicinal All-Carbon Quaternary Centers via Iridium-Catalyzed Allylic Alkylation

J. Caleb Hethcox et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2018)

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Article Chemistry, Multidisciplinary

Efficient and stereodivergent synthesis of unsaturated acyclic fragments bearing contiguous stereogenic elements

Jeffrey Bruffaerts et al.

NATURE CHEMISTRY (2018)

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Article Multidisciplinary Sciences

Stereodivergent synthesis of 1,4-dicarbonyls by traceless charge-accelerated sulfonium rearrangement

Dainis Kaldre et al.

SCIENCE (2018)

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Article Multidisciplinary Sciences

Deconstructive diversification of cyclic amines

Jose B. Roque et al.

NATURE (2018)

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Article Chemistry, Multidisciplinary

Directed Rh-I-Catalyzed Asymmetric Hydroboration of Prochiral 1-Arylcycloprop-2-Ene-1-Carboxylic Acid Derivatives

Andrew Edwards et al.

CHEMISTRY-A EUROPEAN JOURNAL (2018)

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Article Chemistry, Multidisciplinary

Diastereoselective Borocyclopropanation of Allylic Ethers Using a Boromethylzinc Carbenoid

Guillaume Benoit et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2017)

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Article Multidisciplinary Sciences

A unique Pd-catalysed Heck arylation as a remote trigger for cyclopropane selective ring-opening

Sukhdev Singh et al.

NATURE COMMUNICATIONS (2017)

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Article Chemistry, Multidisciplinary

A catalytic enantioselective approach to tetrol bearing vicinal all-carbon quaternary stereogenic centers

Hui Yang et al.

CHEMICAL COMMUNICATIONS (2017)

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Review Chemistry, Multidisciplinary

Copper mediated carbometalation reactions

D. S. Mueller et al.

CHEMICAL SOCIETY REVIEWS (2016)

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Article Chemistry, Multidisciplinary

Diastereodivergent combined carbometalation/zinc homologation/C-C fragmentation reaction as an efficient tool to prepare acyclic allylic quaternary carbon stereocenters

Sudipta Raha Roy et al.

CHEMICAL SCIENCE (2016)

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Article Chemistry, Multidisciplinary

Modulable and Highly Diastereoselective Carbometalations of Cyclopropenes

Dorian Didier et al.

CHEMISTRY-A EUROPEAN JOURNAL (2014)

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Article Chemistry, Multidisciplinary

Congested C-C Bonds by Pd-Catalyzed Enantioselective Allyl-Allyl Cross-Coupling, a Mechanism-Guided Solution

Michael J. Ardolino et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2014)

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Article Chemistry, Multidisciplinary

Construction of Multiple, Contiguous Quaternary Stereocenters in Acyclic Molecules by Lithiation-Borylation

Charlotte G. Watson et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2014)

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Article Chemistry, Multidisciplinary

Copper-Catalyzed Diastereo- and Enantioselective Desymmetrization of Cyclopropenes: Synthesis of Cyclopropylboronates

Alejandro Parra et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2014)

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Article Chemistry, Organic

Copper(I)-catalyzed enantioselective hydroboration of cyclopropenes: facile synthesis of optically active cyclopropylboronates

Bing Tian et al.

ORGANIC CHEMISTRY FRONTIERS (2014)

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Article Chemistry, Multidisciplinary

Enantio-, Diastereo-, and Regioselective Iridium-Catalyzed Asymmetric Allylic Alkylation of Acyclic β-Ketoesters

Wen-Bo Liu et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2013)

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Article Chemistry, Multidisciplinary

Gold(I)-Catalyzed Asymmetric Cyclopropenation of Internal Alkynes

John F. Briones et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2012)

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Article Chemistry, Multidisciplinary

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

Takayuki Goto et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2011)

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Article Chemistry, Multidisciplinary

Enantioselective Cyclopropenation of Alkynes with Acceptor/Acceptor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis

Xin Cui et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2011)

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Article Chemistry, Multidisciplinary

Enantioenriched Synthesis of Cyclopropenes with a Quaternary Stereocenter, Versatile Building Blocks

Misaki Uehara et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2011)

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Article Chemistry, Organic

Rh2(S-PTAD)4-catalyzed asymmetric cyclopropenation of aryl alkynes

John F. Briones et al.

TETRAHEDRON (2011)

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Article Chemistry, Multidisciplinary

Enantioselective Synthesis of trans-Aryl- and -Heteroaryl-Substituted Cyclopropylboronates by Copper(I)-Catalyzed Reactions of Allylic Phosphates with a Diboron Derivative

Chongmin Zhong et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2010)

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Article Chemistry, Multidisciplinary

Highly Enantioselective Rh2(S-DOSP)4-Catalyzed Cyclopropenation of Alkynes with Styryldiazoacetates

John F. Briones et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2010)

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Article Chemistry, Organic

Branched Alkanes Have Contrasting Stabilities

Jerome F. Gonthier et al.

ORGANIC LETTERS (2010)

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Article Chemistry, Multidisciplinary

Synthesis of optically active boron-silicon bifunctional cyclopropane derivatives through enantioselective copper(I)-catalyzed reaction of allylic carbonates with a diboron derivative

Hajime Ito et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2008)

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Article Chemistry, Multidisciplinary

Enantioselective Claisen rearrangements with a hydrogen-bond donor catalyst

Christopher Uyeda et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2008)

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A chiral primary amine thiourea catalyst for the highly enantioselective direct conjugate addition of alpha,alpha-disubstituted aldehydes to nitroalkenes

Mathieu P. Lalonde et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2006)

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Dirhodium(II) tetra(N-(dodecyl benzenesulfonyl)prolinate) catalyzed enantioselective cyclopropenation of alkynes

HML Davies et al.

ORGANIC LETTERS (2004)

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A new chiral Rh(II) catalyst for enantioselective [2+1]-cycloaddition. Mechanistic implications and applications

Y Lou et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2004)

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Enantioselective Michael additions to α,β-unsaturated imides catalyzed by a Salen-Al complex

MS Taylor et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2003)

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Article Chemistry, Multidisciplinary

Catalytic enantioselective hydroboration of cyclopropenes

M Rubina et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2003)

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Borylated Cyclopropanes as Spring-Loaded Entities: Access to Vicinal Tertiary and Quaternary Carbon Stereocenters in Acyclic Systems

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