Organic Chemistry Portal
Organic Chemistry Highlights

Monday, February 13, 2012
Douglass F. Taber
University of Delaware

Enantioselective Synthesis of Alcohols and Amines: The Ichikawa Synthesis of (+)-Geranyllinaloisocyanide

Shuichi Nakamura of the Nagoya Institute of Technology reduced (Angew. Chem. Int. Ed. 2011, 50, 2249. DOI: 10.1002/anie.201007568) the α-oxo ester 1 to 2 with high ee. Günter Helmchen of the Universität-Heidelberg optimized (J. Am. Chem. Soc. 2011, 133, 2072. DOI: 10.1021/ja109953v) the Ir*-catalyzed rearrangement of 3 to the allylic alcohol 4. D. Tyler McQuade of Florida State University effected (J. Am. Chem. Soc. 2011, 133, 2410. DOI: 10.1021/ja1112518) the enantioselective allylic substitution of 5 to give the secondary allyl boronate, that was then oxidized to 6. Kazuaki Kudo of the University of Tokyo developed (Org. Lett. 2011, 13, 3498. DOI: 10.1021/ol2012956) the tandem oxidation of the aldehyde 7 to the α-alkoxy acid 8.

Takashi Ooi of Nagoya University prepared (Synlett 2011, 1265. DOI: 10.1055/s-0030-1260541) the secondary amine 10 by the enantioselective addition of an aniline to the nitroalkene 9. Yixin Lu of the National University of Singapore assembled (Org. Lett. 2011, 13, 2638. DOI: 10.1021/ol200747x) the α-quaternary amine 13 by the addition of the aldehyde 11 to the azodicarboxylate 10.

Chan-Mo Yu of Sungkyunkwan University added (Chem. Commun. 2011, 47, 3811. DOI: 10.1039/C0CC05751G) the enantiomerically-pure 2-borylbutadiene 15 to the aldehyde 14, to give 16 in high ee. Since the allene is readily dragged out to the terminal alkyne, this is also a protocol for the enantioselective homopropargylation of an aldehyde. Lin Pu of the University of Virginia devised (Angew. Chem. Int. Ed. 2011, 50, 2368. DOI: 10.1002/anie.201007351) a protocol for the enantioselective addition of 17 to the aldehyde 18, to give 19. Xiaoming Feng of Sichuan University developed (Angew. Chem. Int. Ed. 2011, 50, 2573. DOI: 10.1002/anie.201007145) a Mg catalyst for the enantioselective addition of 21 to the α-oxo ester 20. Tomonori Misaka and Takashi Sugimura of the University of Hyogo added (J. Am. Chem. Soc. 2011, 133, 5695. DOI: 10.1021/ja200283n) 23 to 24 to give the Z-amide 25 in high ee.

Marc L. Snapper and Amir H. Hoveyda of Boston College developed (J. Am. Chem. Soc. 2011, 133, 3332. DOI: 10.1021/ja200311n) a Cu catalyst for the enantioselective allylation of the imine 26. Jonathan Clayden of the University of Manchester effected (Org. Lett. 2010, 12, 5442. DOI: 10.1021/ol102155h) the enantioselective rearrangement of the amide 29 to the α-quaternary amine 30.

(+)-Geranyllinaloisocyanide (33) had been reported, but the absolute configuration was not known. Yoshiyasu Ichikawa of Kochi University established (Org. Lett. 2011, 13, 2520. DOI: 10.1021/ol200308m) the α-quaternary aminated center of 33 by rearranging 31 to 32.

D. F. Taber, Org. Chem. Highlights 2012, February 13.