Arine und Cyclohexin in der Naturstoffsynthese

Abstract

Erick M. Carreira wurde 1963 in Havanna, Kuba geboren. Er studierte Chemie an der University of Urbana-Champaign (BSc bei Scott Denmark) und promovierte an der Harvard University bei David A. Evans. Es folgte ein Postdoktorat bei Peter Dervan am California Institute of Technology, wo er sich der dortigen Chemiefakultät anschloss. Seit 1998 ist er Professor an der ETH Zürich.Schema 1. Reagentien und Bedingungen: a) AgClO 4 , À10 8C, MS 4 , CH 2 Cl 2 , 86 %, d.r. = 26:1; b) Tf 2 O, iPr 2 NEt, CH 2 Cl 2 , À78 8C, 1 h, 99 %; c) nBuLi, 2-Methoxyfuran, THF, À78 8C, 10 min, 88 %; d) 2-Iod-3-methoxy-5-methylbenzoylchlorid, iPr 2 NEt, DMAP, THF, RT, 2 h, 91 %; e) [(Ph 3 P)PdCl 2 ] (26 Mol-%), NaOAc, DMA, 125 8C, 5 h, 90 %; f) H 2 , Pd/C (10 Mol-%), MeOH, THF, RT, 5 h, 90 %. MS = Molekularsieb, Tf 2 O = Trifluormethansulfonsäureanhydrid, DMAP = N,N-Dimethylaminopyridin. . Angewandte Kurzaufsätze E. M. Carreira und C. M. Gampe Schema 2. Reagentien und Bedingungen: a) TsCl, NEt 3 , DMAP, CH 2 Cl 2 ; b) nBuLi, À78 8C, 3-Lithiofuran, BF 3 OEt 2 , THF, 76 % (2 Stufen); c) KH, BnBr, DMF, 99 %; d) NBS, DMF, 86 %; e) nBuLi, THF, À78 8C, Me 2 Si(Cl)CH=CH 2 , 87 %; f) 9-BBN, THF, H 2 O 2 , NaOH, 96 %; g) 3-Lithiofuran, THF, À78 8C; HCl, EtOH, dann NaCNBH 3 , HCl, 50 8C, 80 %; h) LDA, THF, À78 8C, Me 2 Si(Cl)CH=CH 2 , 70 %; i) 9-BBN, THF, H 2 O 2 , NaOH, 94 %; j) 12, 15, DIAD, PPh 3 , THF, 75 %; k) HF·py, THF, 85 %; l) 14, DIAD, PPh 3 , THF, 85 %; m) nBuLi (3.0 ¾quiv.), Et 2 O, À20 8C, 85 %; n) KOH, DMF/H 2 O; HCl, EtOH, 34 %; o) CAN, MeCN, H 2 O, À15 8C, 74 %; p) IBX, EtOAc, 80 8C; NaClO 2 , NaH 2 PO 4 , 2-Methyl-2-buten, 70 %; q) BBr 3 , CH 2 Cl 2 , À78 8C; MeOH, HCl, 71 %. TsCl = Tosylchlorid, DMF = Me 2 NCHO, 9-BBN = 9-Borabicyclononan, THF = Tetrahydrofuran, DIAD = Diisopropyldiazodicarboxylat, CAN = (NH 4 ) 2 Ce(NO 3 ) 6 , IBX = 2-Iodoxybenzoesäure.

Heteroannulation of Arynes with α‐Amino Imides: Synthesis of 2,2‐Disubstituted Indolin‐3‐ones and Application to the Enantioselective Total Synthesis of (+)‐Hinckdentine A

“…[5] As ac ontinuation of our research program dealing with the total synthesis of indoline-based polycyclic natural products, [6] we became interested in (+ +)-hinckdentine A( 1). [8,9] Thelatter could in turn be synthesized by organocatalytic enantioselective Michael addition of methyl a-isocyano acetate 6 to phenyl vinyl selenone (7). [8,9] Thelatter could in turn be synthesized by organocatalytic enantioselective Michael addition of methyl a-isocyano acetate 6 to phenyl vinyl selenone (7).…”

Synthetic Applications and Methodological Developments of Donor−Acceptor Cyclopropanes and Related Compounds

“…[53] Furthermore, our mechanistic hypothesis has been invoked by numerous groups in recent disclosures of aryne insertion reactions. [54] …”

Gold-catalyzed cyclotrimerization of arynes for the synthesis of triphenylenes

“…Aryne chemistry has been of particular interest due to its high reactivity and broad applications in organic synthesis [1][2][3][4]. Recently, transition metal-catalyzed reactions involving arynes, which are generated by fluoride-induced elimination of Kobayashi's silylaryl triflate under mild conditions [5], have been well documented [6][7][8][9][10][11][12][13][14][15][16][17].…”