Organic Chemistry Portal
Organic Chemistry Highlights

Monday, March 30, 2015
Douglass F. Taber
University of Delaware

Reactions of Alkenes

The catalytic reduction of the alkene 1 gave the cis-fused product (not illustrated), by kinetic H2 addition to the less congested face of the alkene. Ryan A. Shenvi of Scripps La Jolla found (J. Am. Chem. Soc. 2014, 136, 1300. DOI: 10.1021/ja412342g) conditions for stepwise hydrogen atom transfer (HAT), converting 1 to the thermodynamically-favored trans-fused ketone 2. Seth B. Herzon of Yale University devised (J. Am. Chem. Soc. 2014, 136, 6884. DOI: 10.1021/ja502885c) a protocol for the reduction of the double bond of a haloalkene 3 to give the saturated halide 5. The Shenvi conditions also reduced a haloalkene to the saturated halide.

Daniel J. Weix of the University of Rochester and Patrick L. Holland, also of Yale University, established (J. Am. Chem. Soc. 2014, 136, 945. DOI: 10.1021/ja408238n) conditions for the kinetic isomerization of a terminal alkene 6 to the Z internal alkene 7. Christoforos G. Kokotos of the University of Athens showed (J. Org. Chem. 2014, 79, 4270. DOI: 10.1021/jo5003938) that the ketone 9, used catalytically, markedly accelerated the Payne epoxidation of 8 to 10. Note that Helena M. C. Ferraz of the Universidade of São Paulo reported (Tetrahedron Lett. 2000, 41, 5021. DOI: 10.1039/C3SC52533C) several years ago that alkene epoxidation was also easily carried out with DMDO generated in situ from acetone and oxone.

Theodore A. Betley of Harvard University prepared (Chem. Sci. 2014, 5, 1526. DOI: 10.1039/C3SC52533C) the allylic amine 12 by reacting the alkene 11 with 1-azidoadamantane in the presence of an iron catalyst. Rodney A. Fernandes of the Indian Institute of Technology Bombay developed (J. Org. Chem. 2014, 79, 5787. DOI: 10.1021/jo500921j) efficient conditions for the Wacker oxidation of a terminal alkene 6 to the methyl ketone 13. Yong-Qiang Wang of Northwest University oxidized (Org. Lett. 2014, 16, 1610. DOI: 10.1021/ol500218p) the alkene 6 to the enone 14. Peili Teo of the National University of Singapore devised (Chem. Commun. 2014, 50, 2608. DOI: 10.1039/C3CC48810A) conditions for the Marvovnikov hydration of the alkene 6 to the alcohol 15. Internal alkenes were inert under these conditions, but Yoshikazo Kitano of the Tokyo University of Agriculture and Technology effected (Synthesis 2014, 46, 1455. DOI: 10.1055/s-0033-1338605) the Markovnikov amination (not illustrated) of more highly substituted alkenes.

Andrei V. Malkov of Loughborough University and Pavel Kocovsky of Stockholm University converted (Chem. Eur. J. 2014, 20, 4542. DOI: 10.1002/chem.201304798) the alkene 16 to the unsaturated ester 17. Guangbin Dong of the University of Texas at Austin showed (Science 2014, 345, 68. DOI: 10.1126/science.1254465) that a ketone 18 could be alkylated with an alkene 11, leading to the α-alkyl ketone 19. Uttam K. Tambar of UT Southwestern Medical Center activated (Angew. Chem. Int. Ed. 2014, 53, 1664. DOI: 10.1002/anie.201309134) the alkene 20 by exposure to the commercial reagent 21, then directly coupled that intermediate product with a Grignard reagent 22 to give 23.

M. Christina White of the University of Illinois oxidized (J. Am. Chem. Soc. 2014, 136, 5750. DOI: 10.1021/ja500726e) the alkene 24 in the presence of 25 to give the coupled product 26. Shang-Dong Yang of Lanzhou University showed (Org. Lett. 2014, 16, 3118. DOI: 10.1021/ol501247b) that the electron-deficient arene 27 could couple with 24 under oxidative conditions, leading to 28. Phil S. Baran, also of Scripps La Jolla, assembled (J. Am. Chem. Soc. 2014, 136, 1304. DOI: 10.1021/ja4117632) the ketone 31 by adding the alkene 29 in a conjugate sense to the enone 30.

D. F. Taber, Org. Chem. Highlights 2015, March 30.