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Preparation of Distant Quaternary Carbon Stereocenters by Double Selective Ring-Opening of 1,1-Biscyclopropyl Methanol Derivatives

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Specialty Chemistry
Date 2022 May 6
PMID 35521738
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Abstract

The diastereoselective double carbometalation reaction of cyclopropenes provides, in a single-pot operation, two ω-ene-[1,1]-bicyclopropyl ester derivatives. One regioisomer then undergoes a Pd-catalyzed addition of aryl iodide to provide skipped dienes possessing several distant stereocenters including two congested quaternary carbon centers with excellent diastereoselectivity.

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Preparation of Distant Quaternary Carbon Stereocenters by Double Selective Ring-Opening of 1,1-Biscyclopropyl Methanol Derivatives.

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References
1.
Amatore C, Jutand A . Anionic Pd(0) and Pd(II) intermediates in palladium-catalyzed Heck and cross-coupling reactions. Acc Chem Res. 2000; 33(5):314-21. DOI: 10.1021/ar980063a. View

2.
Larsen C, Erdogan G, Grotjahn D . General catalyst control of the monoisomerization of 1-alkenes to trans-2-alkenes. J Am Chem Soc. 2014; 136(4):1226-9. DOI: 10.1021/ja411438d. View

3.
Qin Y, Stivala C, Zakarian A . Acyclic stereocontrol in the Ireland-Claisen rearrangement of alpha-branched esters. Angew Chem Int Ed Engl. 2007; 46(39):7466-9. DOI: 10.1002/anie.200702142. View

4.
Larionov E, Li H, Mazet C . Well-defined transition metal hydrides in catalytic isomerizations. Chem Commun (Camb). 2014; 50(69):9816-26. DOI: 10.1039/c4cc02399d. View

5.
Marek I, Minko Y, Pasco M, Mejuch T, Gilboa N, Chechik H . All-carbon quaternary stereogenic centers in acyclic systems through the creation of several C-C bonds per chemical step. J Am Chem Soc. 2014; 136(7):2682-94. DOI: 10.1021/ja410424g. View