Synthesis of 2,3-Disubstituted 1,3-Butadienes from Organotin Precursors and Butadienyllithium Reagents
J. Am. Chem. SOC.1993,115, 6625-6635 6625 Synthesis of 2,3-Disubstituted 1,3-Butadienes from Organotin Precursors and Butadienyllithium Reagents. Diels-Alder Reactivity' Hans J. Reich,' Ieva L. Reich, Kenneth E. Yelm, Johnathan E. Holladay, and David Gschneidner Contributionfrom the Samuel H. McElvain Laboratories of Organic Chemistry, Department of Chemistry, University of Wisconsin, Madison. Wisconsin 53706 Received February 22, 1993 Abstracf: 1,4-Bis(trimethylstanny1)-2-butyne (1) and 2,3-bis(trimethylstannyl)-1,3-butadiene (2), versatile synthons for the 2,3-dianion of 1,3-butadiene,have been prepared from either 1,Cdichloro-Zbutyne or 2,3-dichloro- 1,3-butadiene by reaction with 2 equiv of (trimethylstanny1)lithium. At -78 OC, the kinetic product from either dichloro precursor is 1which can be isomerized to 2. The monolithium species formed from 1 and 2 have been characterized by 13C NMR. One equivalent of methyllithium added to 1 at -78 OC forms 2-lithio-l-(trimethylstannyl)-2,3-butadiene(5), while 2 forms 2-lithio-3-(trimethylstannyl)-1,3-butadiene(6). A second equivalent of methyllithium converts 5 to a dilithio species, 7, whose NMR spectrum is consistent with (LiCH2CWCH2Li),. The reagent 6 slowly isomerizes to 5 at -50 OC and also forms 7 at this temperature when excess methyllithium is present. 2-Lithio diene 6 (and the cuprate and Grignard reagent prepared from it) is a convenient starting material for the preparation of numerous 2-x-3- (trimethylstanny1)-1,3-butadienes by reaction with electrophiles such as halosilanes, disulfides, selenium, alkyl halides, positive halogen sources, aldehydes, and ketones.
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