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Literature DB >> 22876797

Steric effects compete with aryne distortion to control regioselectivities of nucleophilic additions to 3-silylarynes.

Sarah M Bronner¹, Joel L Mackey, K N Houk, Neil K Garg.

Abstract

We report an experimental and computational study of 3-silylarynes. The addition of nucleophiles yield ortho-substituted products as a result of aryne distortion, but meta-substituted products form predominately when the nucleophile is large. Computations correctly predict the preferred site of attack observed in both nucleophilic addition and cycloaddition experiments. Nucleophilic additions to 3-tert-butylbenzyne, which is not significantly distorted, give meta-substituted products.

Entities: Chemical Gene

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Year: 2012 PMID： 22876797 PMCID： PMC3445038 DOI： 10.1021/ja306723r

Source DB: PubMed Journal: J Am Chem Soc ISSN： 0002-7863 Impact factor: 15.419

28 in total

Review 1. A comprehensive history of arynes in natural product total synthesis.

Authors: Pamela M Tadross; Brian M Stoltz
Journal: Chem Rev Date: 2012-03-23 Impact factor: 60.622

2. Stereoinduction by distortional asymmetry.

Authors: Robert V Kolakowski; Lawrence J Williams
Journal: Nat Chem Date: 2010-02-28 Impact factor: 24.427

3. Origin of regioselectivity in palladium-catalyzed cross-coupling reactions of polyhalogenated heterocycles.

Authors: Claude Y Legault; Yeimy Garcia; Craig A Merlic; K N Houk
Journal: J Am Chem Soc Date: 2007-10-03 Impact factor: 15.419

4. Distortion/interaction energy control of 1,3-dipolar cycloaddition reactivity.

Authors: Daniel H Ess; K N Houk
Journal: J Am Chem Soc Date: 2007-08-09 Impact factor: 15.419

5. Modular approach to silicon-bridged biaryls: palladium-catalyzed intramolecular coupling of 2-(arylsilyl)aryl triflates.

Authors: Masaki Shimizu; Kenji Mochida; Tamejiro Hiyama
Journal: Angew Chem Int Ed Engl Date: 2008 Impact factor: 15.336

6. Indolyne experimental and computational studies: synthetic applications and origins of selectivities of nucleophilic additions.

Authors: G-Yoon J Im; Sarah M Bronner; Adam E Goetz; Robert S Paton; Paul H-Y Cheong; K N Houk; Neil K Garg
Journal: J Am Chem Soc Date: 2010-11-29 Impact factor: 15.419

7. Facile N-arylation of amines and sulfonamides and o-arylation of phenols and arenecarboxylic acids.

Authors: Zhijian Liu; Richard C Larock
Journal: J Org Chem Date: 2006-04-14 Impact factor: 4.354

8. Indolyne and aryne distortions and nucleophilic regioselectivites.

Authors: Paul H-Y Cheong; Robert S Paton; Sarah M Bronner; G-Yoon J Im; Neil K Garg; K N Houk
Journal: J Am Chem Soc Date: 2010-02-03 Impact factor: 15.419

9. Enantioselective, thiourea-catalyzed intermolecular addition of indoles to cyclic N-acyl iminium ions.

Authors: Emily A Peterson; Eric N Jacobsen
Journal: Angew Chem Int Ed Engl Date: 2009 Impact factor: 15.336

10. A novel α,β-unsaturated nitrone-aryne [3+2] cycloaddition and its application in the synthesis of the cortistatin core.

Authors: Mingji Dai; Zhang Wang; Samuel J Danishefsky
Journal: Tetrahedron Lett Date: 2008-11-17 Impact factor: 2.415

19 in total

Steric effects compete with aryne distortion to control regioselectivities of nucleophilic additions to 3-silylarynes.

Review 1. A comprehensive history of arynes in natural product total synthesis.

2. Stereoinduction by distortional asymmetry.

3. Origin of regioselectivity in palladium-catalyzed cross-coupling reactions of polyhalogenated heterocycles.

4. Distortion/interaction energy control of 1,3-dipolar cycloaddition reactivity.

5. Modular approach to silicon-bridged biaryls: palladium-catalyzed intramolecular coupling of 2-(arylsilyl)aryl triflates.

6. Indolyne experimental and computational studies: synthetic applications and origins of selectivities of nucleophilic additions.

7. Facile N-arylation of amines and sulfonamides and o-arylation of phenols and arenecarboxylic acids.

8. Indolyne and aryne distortions and nucleophilic regioselectivites.

9. Enantioselective, thiourea-catalyzed intermolecular addition of indoles to cyclic N-acyl iminium ions.

10. A novel α,β-unsaturated nitrone-aryne [3+2] cycloaddition and its application in the synthesis of the cortistatin core.

1. Expanding the ROMP Toolbox: Synthesis of Air-Stable Benzonorbornadiene Polymers by Aryne Chemistry.

2. Computational predictions of substituted benzyne and indolyne regioselectivities.

3. Quantification of the Electrophilicity of Benzyne and Related Intermediates.

4. Expanding the Strained Alkyne Toolbox: Generation and Utility of Oxygen-Containing Strained Alkynes.

5. Generation and regioselective trapping of a 3,4-piperidyne for the synthesis of functionalized heterocycles.

Review 6. Hexadehydro-Diels-Alder Reaction: Benzyne Generation via Cycloisomerization of Tethered Triynes.

7. Origins of Endo Selectivity in Diels-Alder Reactions of Cyclic Allene Dienophiles.

8. The Aryne Phosphate Reaction.

9. Diels-Alder construction of regiodifferentiated meta-amino phenols and derivatives.

10. The role of aryne distortions, steric effects, and charges in regioselectivities of aryne reactions.