title: Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs.
abstract: The formation of alkylidenezinc carbenoids by 1,4-addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with β-(propargyloxy)enoates having pendant iodo- and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is fully stereoselective at -30 °C and arises from a formal anti-selective carbozincation reaction. Upon warming, the zinc carbenoid is stereochemically labile and isomerizes to its more stable form.
authors: Institut Parisien de Chimie Moléculaire (UMR 7201), FR 2769, UPMC Univ Paris 06, CNRS, Bâtiment F 2ème et., Case 183, 4 place Jussieu, F-75005 Paris, France.
authors: Fabrice
authors: F
authors: Chemla
authors: Florian
authors: F
authors: Dulong
authors: Franck
authors: F
authors: Ferreira
authors: Alejandro
authors: A
authors: Pérez-Luna
keywords: carbenoids; carbometallation; carbozincation; radicals; tandem reaction
references: J Am Chem Soc. 2007 Dec 12;129(49):15405-9
references: 17988132
references: Chemistry. 2011 Feb 1;17(5):1586-95
references: 21268161
references: Angew Chem Int Ed Engl. 2003 Sep 5;42(34):4043-6
references: 12973764
references: Chemistry. 2006 Aug 25;12(25):6506-13
references: 16789032
references: Chem Rev. 2010 Apr 14;110(4):2366-447
references: 20196544
references: Angew Chem Int Ed Engl. 2008;47(41):7888-91
references: 18773401
references: Org Lett. 2010 Jul 2;12(13):3026-9
references: 20515018
references: Chem Commun (Camb). 2009 Jan 28;(4):469-70
references: 19137188
references: Org Lett. 2000 Jun 1;2(11):1593-5
references: 10841487
references: Angew Chem Int Ed Engl. 2009;48(38):7017-20
references: 19691076
references: Chemistry. 2012 Mar 12;18(11):3241-7
references: 22328494
references: Org Lett. 2000 Feb 24;2(4):419-21
references: 10814340
references: Acc Chem Res. 2009 Feb 17;42(2):345-55
references: 19113862
references: J Am Chem Soc. 2003 Oct 22;125(42):12698-9
references: 14558804
references: Org Lett. 2010 Aug 20;12(16):3590-3
references: 20666447
references: J Org Chem. 2007 Jan 19;72(2):398-406
references: 17221954
references: J Org Chem. 2012 Jul 6;77(13):5775-80
references: 22667329
references: J Am Chem Soc. 2009 Mar 25;131(11):3802-3
references: 19253939
references: Angew Chem Int Ed Engl. 2006 Jul 17;45(29):4826-9
references: 16795096
references: Chem Commun (Camb). 2008 Jul 28;(28):3317-8
references: 18622456
references: Chem Rev. 2000 Aug 9;100(8):2887-900
references: 11749308
references: Angew Chem Int Ed Engl. 2008;47(3):573-6
references: 18034439
references: Inorg Chem. 2007 May 14;46(10):4293-7
references: 17417835
references: Org Lett. 2011 Apr 1;13(7):1884-7
references: 21388206
references: Angew Chem Int Ed Engl. 2008;47(7):1317-9
references: 18176931
references: Chem Commun (Camb). 2009 Jan 8;(2):215-7
references: 19099073
references: Angew Chem Int Ed Engl. 2006 Apr 28;45(18):2951-4
references: 16555342
references: J Am Chem Soc. 2012 Aug 8;134(31):13018-26
references: 22839354
references: Chemistry. 2008;14(29):8784-8
references: 18752234