Organic Chemistry Portal
Organic Chemistry Highlights

Monday, March 17, 2014
Allison K. Griffith and Tristan H. Lambert
Columbia University


The α-C-H functionalization of piperidine catalyzed by tantalum complex 1 to produce amine 2 was developed (Org. Lett. 2013, 15, 2182. DOI: 10.1021/ol400729v) by Laurel L. Schafer at the University of British Columbia. An asymmetric diamination of diene 3 with diaziridine reagent 4 under palladium catalysis to furnish cyclic sulfamide 5 was developed (Org. Lett. 2013, 15, 796. DOI: 10.1021/ol303469a) by Yian Shi at Colorado State University. Enantioenriched β-fluoropiperdine 8 was prepared (Angew. Chem. Int. Ed. 2013, 52, 2469. DOI: 10.1002/anie.201208471) via aminofluorocyclization with hypervalent iodide 7, as reported by Cristina Nevado at the University of Zürich. Erick M. Carreira at ETH Zürich disclosed (J. Am. Chem. Soc. 2013, 135, 6814. DOI: 10.1021/ja4026787) a ruthenium-catalyzed hydrocarbamoylation of allylic formamide 9 to yield pyrrolidone 10.

Hans-Günther Schmalz at the University of Köln disclosed (Angew. Chem. Int. Ed. 2013, 52, 1576. DOI: 10.1002/anie.201208082) an asymmetric hydrocyanation of styrene with Ni(cod)2 and phosphine-phosphite ligand 12 to yield exclusively the branched cyanide 13. A similar transformation of styrene to the hydroxycarbonylated product 15 was catalyzed (Chem. Commun. 2013, 49, 3306. DOI: 10.1039/C3CC41291A) by palladium complex 14, as reported by Matthew L. Clarke at the University of St Andrews.

Feng-Ling Qing at the Chinese Academy of Sciences found (Angew. Chem. Int. Ed. 2013, 52, 2198. DOI: 10.1002/anie.201208971) that the hydrotrifluoromethylation of unactivated alkene 16 was catalyzed by silver nitrate. The same transformation was also reported (J. Am. Chem. Soc. 2013, 135, 2505. DOI: 10.1021/ja401022x) by Veronique Gouverneur at the University of Oxford using a ruthenium photocatalyst and the Umemoto reagent 18.

Clark R. Landis at the University of Wisconsin-Madison reported (Angew. Chem. Int. Ed. 2013, 52, 1564. DOI: 10.1002/anie.201208819) a one-pot asymmetric hydroformylation and Wittig olefination to transform alkene 19 into γ-chiral α,β-unsaturated carbonyl compound 20. Debabrata Mati at the Indian Institute of Technology Bombay found (J. Am. Chem. Soc. 2013, 135, 3355. DOI: 10.1021/ja311942e) that alkene 22 could be nitrated stereoselectively with silver nitrite and TEMPO to form alkene 23.

Damian W. Young at the Broad Institute disclosed (Org. Lett. 2013, 15, 1218. DOI: 10.1021/ol400134d) that a macrocyclic vinylsiloxane 24, which was synthesized via an E-selective ring closing metathesis reaction, could be functionalized to make either E- or Z-alkenes, 25 and 26.

A ruthenium catalyst 28 exhibiting Z-selectivity for the homodimerization of alkene 27 was disclosed (J. Am. Chem. Soc. 2013, 135, 1276. DOI: 10.1021/ja311916m) by Robert H. Grubbs at Caltech. Meanwhile, a Z-selective cross metathesis of vinyl-B(pin) (30) and alkene 32 with a molybdenum catalyst 31 was disclosed (J. Am. Chem. Soc. 2013, 135, 6026. DOI: 10.1021/ja403188t) by Amir H. Hoveyda at Boston College.

A. K. Griffith, T. H. Lambert, Org. Chem. Highlights 2014, March 17.