Reactions of Alkenes

Abstract

Paul J. Chirik at Princeton University reported (Science 2012, 335, 567) an iron catalyst that hydrosilylates alkenes with anti-Markovnikov selectivity, as in the conversion of 1 to 2. A regioselective hydrocarbamoylation of terminal alkenes was developed (Chem. Lett. 2012, 41, 298) by Yoshiaki Nakao at Kyoto University and Tamejiro Hiyama at Chuo University, which allowed for the chemoselective conversion of diene 3 to amide 4. Gojko Lalic at the University of Washington reported (J. Am. Chem. Soc. 2012, 134, 6571) the conversion of terminal alkenes to tertiary amines, such as 5 to 6, with anti-Markovnikov selectivity by a sequence of hydroboration and copper-catalyzed amination. Related products such as 8 were prepared (Org. Lett. 2012, 14, 102) by Wenjun Wu at Northwest A&F University and Xumu Zhang at Rutgers via an isomerization-hydroaminomethylation of internal olefin 7. Seunghoon Shin at Hanyang University (experimental work) and Zhi-Xiang Yu at Peking University (computational work) reported (J. Am. Chem. Soc. 2012, 134, 208) that 9 could be directly converted to bicyclic lactone 11 with propiolic acid 10 using gold catalysis. A nickel/Lewis acid multicatalytic system was found (Angew. Chem. Int. Ed. 2012, 51, 5679) by the team of Professors Nakao and Hiyama to effect the addition of pyridones to alkenes, such as in the conversion of 12 to 13. Radical-based functionalization of alkenes using photoredox catalysis was developed (J. Am. Chem. Soc. 2012, 134, 8875) by Corey R.J. Stephenson at Boston University, an example of which was the addition of bromodiethyl malonate across alkene 14 to furnish 15. Samir Z. Zard at Ecole Polytechnique reported (Org. Lett. 2012, 14, 1020) that the reaction of xanthate 17 with terminal alkene 16 led to the product 18. The radical-based addition of nucleophiles including azide to alkenes with Markovnikov selectivity (cf. 19 to 20) was reported (Org. Lett. 2012, 14, 1428) by Dale L. Boger at Scripps La Jolla using an Fe(III)/NaBH4-based system. A remarkably efficient and selective catalyst 22 was found (J. Am. Chem. Soc. 2012, 134, 10357) by Douglas B. Grotjahn at San Diego State University for the single position isomerization of alkenes, which effected the transformation of 21 to 23 in only half an hour.