Magical power of transition metals: Past, present, and future (Nobel Lecture)

Angewandte Chemie - International Edition

Volumn 50, Issue 30, 2011, Pages 6738-6764

  Negishi, Ei Ichi ^a  

^a PURDUE UNIVERSITY   (United States)

Author keywords

carbometalation; cross coupling; Negishi coupling; palladium

Indexed keywords

PALLADIUM; SYNTHESIS (CHEMICAL);

CARBOMETALATION; CROSS-COUPLINGS; CURRENT STATUS; HISTORICAL DEVELOPMENT; NEGISHI COUPLING; NOBEL PRIZES; ORGANIC SYNTHESIS; PALLADIUM-CATALYZED CROSS-COUPLINGS;

TRANSITION METALS;

EID: 79960264489     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201101380     Document Type: Article

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137. "Carbometallation reaction of alkynes with organoalane-zirconocene derivatives as a route to stereo- and regio-defined trisubstituted alkenes":, E. Negishi, D. E. Van Horn, T. Yoshida, J. Am. Chem. Soc. 1985, 107, 6639-6647.
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145. "(E)-(2-Bromoethenyl)dibromoborane. A new precursor for (E)-1,2-disubstituted ethenes":, S. Hyuga, Y. Chiba, N. Yamashina, S. Hara, A. Suzuki, Chem. Lett. 1987, 1757-1760.
146. "A stereoselective synthesis of 3,3-disubstituted allylborane derivatives using haloboration reaction and their application to the diastereospecific synthesis of homoallylic alcohols having quaternary carbon":, M. Sato, Y. Yamamoto, S. Hara, A. Suzuki, Tetrahedron Lett. 1993, 34, 7071-7014.
147. "Efficient and stereoselective synthesis of yellow scale pheromone via alkyne haloboration, Zr-catalyzed asymmetric carboalumination of alkenes (ZACA Reaction), and Pd-catalyzed tandem Negishi coupling":, Z. Xu, E. Negishi, Org. Lett. 2008, 10, 4311-4314.
148. C. Wang, T. Tobrman, Z. Xu, E. Negishi, Org. Lett. 2009, 11, 4092-4095
149. "Arylethyne bromoboration-Negishi coupling route to E- or Z-aryl-substituted trisubstituted alkenes of ≥98 % isomeric purity. New horizon in the highly selective synthesis of trisubstituted alkenes":, C. Wang, T. Tobrman, Z. Xu, E. Negishi, Adv. Synth. Catal. 2010, 352, 627-631.
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151. "Cascade radical cyclizations via biradicals generated from (Z)-1,2,4-heptatrien-6-ynes":, K. K. Wang, Z. Wang, A. Tarli, P. Gannett, J. Am. Chem. Soc. 1996, 118, 10783-10791
152. "Synthesis and thermolysis of enediynyl ethyl ethers as precursors of enyne-ketenes":, A. Tarli, K. K. Wang, J. Org. Chem. 1997, 62, 8841-8847.
153. "Highly (>98 %) selective trisubstituted alkene synthesis of wide applicability via fluoride-promoted Pd-catalyzed cross-coupling of alkenylboranes":, E. Negishi, T. Tobrman, H. Rao, S. Xu, C.-T. Lee, Isr. J. Chem. 2010, 50, 696-701.
154. "A convenient synthesis of cis-alkenylboranes and its application to the synthesis of disubstituted trans-alkenes and conjugated cis-enynes":, E. Negishi, R. M. Williams, G. Lew, T. Yoshida, J. Organomet. Chem. 1975, 92, C 4 -C 6
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158. "Highly stereo- and regioselective synthesis of (Z)-trisubstituted alkenes via 1-bromo-1-alkyne hydroboration-migratory insertion-Zn-promoted iodinolysis and Pd-catalyzed organozinc cross-coupling":, Z. Huang, E. Negishi, J. Am. Chem. Soc. 2007, 129, 14788-14792.
159. "Stereoselective synthesis of (Z)-(1-organo-1-alkenyl)boronic esters by the palladium-catalyzed cross-coupling reaction of (Z)-(1-iodo-1-alkenyl) boronic esters with organozinc reagents":, T. Moriya, N. Miyaura, A. Suzuki, Chem. Lett. 1993, 1429-1432.
160. "Reaction of alkenylboronic acids with iodine under the influence of base. Simple procedure for the stereospecific conversion of terminal alkynes into trans-1-alkenyl iodides via hydroboration":, H. C. Brown, T. Hamaoka, N. Ravindran, J. Am. Chem. Soc. 1973, 95, 5786-5788.
161. "Stereospecific conversion of alkenylboronic acids into alkenyl bromides with inversion of configuration. Striking differences in the stereochemistry of the replacement of the boronic acid substituent by bromine and iodine and its significance in terms of the reaction mechanism":, H. C. Brown, T. Hamaoka, N. Ravindran, J. Am. Chem. Soc. 1973, 95, 6456-6457.
162. For the initial thermal isomerization at 150 °C, see "Anti-carbometallation of homopropargyl alcohols and their higher homologues via non-chelation-controlled syn-carbometallation and chelation-controlled isomerization":, S. Ma, E. Negishi, J. Org. Chem. 1997, 62, 784-785.
163. 3-Promoted facile E-to-Z isomerization route to (Z)-2-methyl-1-buten- 1,4-ylidene synthons for highly efficient and selective (Z)-isoprenoid synthesis":, G. Wang, E. Negishi, Eur. J. Org. Chem. 2009, 1679-1682.
164. "A strictly "pair"-selective synthesis of conjugated diynes via Pd-catalyzed cross coupling of 1,3-diynylzincs: A superior alternative to the Cadiot-Chodkiewicz reaction":, E. Negishi, M. Hata, C. Xu, Org. Lett. 2000, 2, 3687-3689.
165. "Zirconium-promoted bicyclization of enynes":, E. Negishi, S. J. Holmes, J. M. Tour, J. A. Miller, J. Am. Chem. Soc. 1985, 107, 2568-2569.
166. 10":, E. Negishi, S. Y. Liou, C. Xu, S. Huo, Org. Lett. 2002, 4, 261-264.
167. "Zirconium-catalyzed enantioselective methylalumination of monosubstituted alkenes":, D. Y. Kondakov, E. Negishi, J. Am. Chem. Soc. 1995, 117, 10771-10772
168. "Zirconium-catalyzed enantioselective alkylalumination of monosubstituted alkenes proceeding via noncyclic mechanism":, D. Y. Kondakov, E. Negishi, J. Am. Chem. Soc. 1996, 118, 1577-1578.
169. "Superelectrophiles":, G. A. Olah, Angew. Chem. 1993, 105, 805-827
170. Angew. Chem. Int. Ed. Engl. 1993, 32, 767-788.
171. "New reaction of α-olefins with diethylmagnesium catalyzed by biscyclopentadienylzirconium chloride":, U. M. Dzhemilev, O. S. Vostrikova, R. M. Sultanov, Izv. Akad. Nauk SSSR Ser. Khim. 1983, 218-220.
172. "An odyssey from stoichiometric carbotitanation of alkynes to zirconium-catalyzed enantioselective carboalumination of alkenes": for a review, see, E. Negishi, D. Y. Kondakov, Chem. Soc. Rev. 1996, 25, 417-426.
173. "Remarkably "pair"-selective and regioselective carbon-carbon bond forming reaction of zirconacylclopentane derivatives with Grignard reagents":, T. Takahashi, T. Seki, Y. Nitto, M. Saburi, C. J. Rousset, E. Negishi, J. Am. Chem. Soc. 1991, 113, 6266-6268.
174. "An investigation of the reaction of bis(cyclopentadienyl)titanium dichlorides with trimethylaluminum. Mechanism of an α-hydrogen abstraction reaction":, K. C. Ott, E. J. M. deBoer, R. H. Grubbs, Organometallics 1984, 3, 223-230.
175. "C-C bond formation (part 1) by addition reactions: through carbometallation mediated by Group 4-7 metals": for a review of this subject, see, E. Negishi, T. Novak, in Comprehensive Organometallic Chemistry III (Ed.:, I. Ojima,), Elsevier, Oxford, 2007, chap. 10.06, pp 251-297.
176. "Zirconium-catalyzed asymmetric carbomagnesiation":, J. P. Morken, M. T. Didiuk, A. H. Hoveyda, J. Am. Chem. Soc. 1993, 115, 6997-6998
177. "Enantio-, diastereo-, and regioselective zirconium-catalyzed carbomagnesiation of cyclic ethers with higher alkyls of magnesium. Utility in synthesis and mechanistic implications":, M. T. Didiuk, C. W. Johannes, J. P. Morken, A. H. Hoveyda, J. Am. Chem. Soc. 1995, 117, 7097-7104.
178. "Catalytic asymmetric carbomagnesiation of unactivated alkenes. A new, effective, active, cheap and recoverable chiral zirconocene":, L. Bell, R. J. Whitby, R. V. H. Jones, M. C. H. Standen, Tetrahedron Lett. 1996, 37, 7139-7142
179. "Synthesis of heterocycles using zirconium-catalyzed asymmetric diene cyclization":, Y. Yamamura, M. Hyakutake, M. Mori, J. Am. Chem. Soc. 1997, 119, 7615-7616.
180. "Novel head-to-tail alkyl-alkene or alkene-alkene coupling via zirconium-catalyzed reaction of alkylmagnesium derivatives with monosubstituted alkenes": for a study of zirconocene-catalyzed alkene carbomagnesiation with longer alkylmagnesium derivatives, see, C. J. Rousset, E. Negishi, N. Suzuki, T. Takahashi, Tetrahedron Lett. 1992, 33, 1965-1968.
181. "The role of torsional isomers of planarly chiral nonbridged bis(indenyl)metal type complexes in stereoselective propene polymerization" :, G. Erker, M. Aulbach, M. Knickmeier, D. Wingbermuhle, C. Krüger, M. Nolte, S. Werner, J. Am. Chem. Soc. 1993, 115, 4590-4601
182. "ansa-Metallocene derivatives. IV. Synthesis and molecular structures of chiral ansa-titanocene derivatives with bridged tetrahydroindenyl ligands":, F. R. W. P. Wild, L. Zsolnai, G. Huttner, H. H. Brintzinger, J. Organomet. Chem. 1982, 232, 233-247
183. "ansa-Metallocene derivatives. VII. Synthesis and crystal structure of a chiral ansa-zirconocene derivative with ethylene-bridged tetrahydroindenyl ligands:, F. R. W. P. Wild, M. Wasiucionek, G. Huttner, H. H. Brintzinger, J. Organomet. Chem. 1985, 288, 63-67
184. Available from Aldrich Chemical Co., Milwaukee, WI.
185. For a recent review, see "Effect of the nature of Metallocene complexes of Group IV metals on their performance in catalytic ethylene and propylene polymerization":, H. G. Alt, A. Koppl, Chem. Rev. 2000, 100, 1205-1222.
186. "Water/MAO acceleration of the zirconocene-catalyzed asymmetric methylalumination of α-olefins":, P. Wipf, S. Ribe, Org. Lett. 2000, 2, 1713-1716
187. "Optical rotation computation, total synthesis, and stereochemistry assignment of the marine natural product Pitiamide A":, S. Ribe, R. K. Kondru, D. N. Beratan, P. Wipf, J. Am. Chem. Soc. 2000, 122, 4608-4617.
188. "A convenient and asymmetric protocol for the synthesis of natural products containing chiral alkyl chains via Zr-catalyzed asymmetric carboalumination of alkenes. Syntheses of phytol and vitamins E and K":, S. Huo, E. Negishi, Org. Lett. 2001, 3, 3253-3256.
189. "A new protocol for the enantioselective synthesis of methyl-substituted chiral alkanols and their derivatives via hydroalumination-zirconium catalyzed alkylalumination tandem process", S. Huo, J. Shi, E. Negishi, Angew. Chem. 2002, 114, 2245-2247
190. Angew. Chem. Int. Ed. 2002, 41, 2141-2143.
191. "An efficient and general method for the synthesis of α,ω-difunctional reduced polypropionates by Zr-catalyzed asymmetric carboalumination: synthesis of the scyphostatin sidechain":, Z. Tan, E. Negishi, Angew. Chem. 2004, 116, 2971-2974
192. Agnew. Chem. Int. Ed. 2004, 43, 2911-2914.
193. "A new, efficient, and general route to reduced polypropionates via Zr-catalyzed asymmetric C-C Bond formation":, E. Negishi, Z. Tan, B. Liang, T. Novak, Proc. Natl. Acad. Sci. USA 2004, 101, 5782-5787.
194. "Efficient and selective synthesis of siphonarienolone and related reduced polypropionates via Zr-catalyzed asymmetric carboalumination":, M. Magnin-Lachaux, Z. Tan, B. Liang, E. Negishi, Org. Lett. 2004, 6, 1425-1427.
195. "Efficient and selective synthesis of 6,7-dehydrostipiamide via Zr-catalyzed asymmetric carboalumination and Pd-catalyzed cross-coupling of organozincs":, X. Zeng, F. Zeng, E. Negishi, Org. Lett. 2004, 6, 3245-3248.
196. "All-catalytic, efficient, and asymmetric synthesis of α,ω-diheterofunctional reduced polypropionates via "one-pot" Zr-catalyzed asymmetric carboalumination-Pd-catalyzed cross-coupling tandem process":, T. Novak, Z. Tan, B. Liang, E. Negishi, J. Am. Chem. Soc. 2005, 127, 2838-2839.
197. "Catalytic, efficient, and syn-selective construction of deoxypolypropionates and other chiral compounds via Zr-catalyzed asymmetric carboalumination of allyl Alcohol":, B. Liang, T. Novak, Z. Tan, E. Negishi, J. Am. Chem. Soc. 2006, 128, 2770-2771.
198. "Zirconium-catalyzed asymmetric carboalumination (ZACA Reaction) of 1,4-dienes":, Z. Tan, B. Liang, S. Huo, J. Shi, E. Negishi, Tetrahedron: Asymmetry 2006, 17, 512-515.
199. "Zirconium-catalyzed carboalumination of alkenes: ZACA-lipase-catalyzed acetylation synergy":, Z. Huang, Z. Tan, T. Novak, G. Zhu, E. Negishi, Adv. Synth. Catal. 2007, 349, 539-545.
200. "Fully reagent-controlled asymmetric synthesis of (-)-spongidepsin via the Zr-catalyzed asymmetric carboalumination of alkenes (ZACA Reaction)":, G. Zhu, E. Negishi, Org. Lett. 2007, 9, 2771-2774.
201. "1,4-Pentenynes as a five-carbon synthon for efficient and selective syntheses of natural products containing 2,4-dimethyl-1-penten-1,5-ylidene and related moieties via Zr-catalyzed carboalumination of alkynes and alkenes":, G. Zhu, E. Negishi, Chem. Eur. J. 2008, 14, 311-318.
202. 1 via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA)-lipase-catalyzed acetylation tandem process":, B. Liang, E. Negishi, Org. Lett. 2008, 10, 193-195.
203. "Efficient and selective synthesis of (S,R,R,S,R,S)-4,6,8,10,16,18- hexamethyldocosane via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA) reaction":, G. Zhu, B. Liang, E. Negishi, Org. Lett. 2008, 10, 1099-1101.
204. "Total synthesis of (+)-scyphostatin featuring an enantioselective and highly efficient route to the side-chain via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA)":, E. Pitsinos, N. Athinaios, Z. Xu, G. Wang, E. Negishi, Chem. Commun. 2010, 46, 2200-2202.
205. "Asymmetric carbometallations", E. Negishi, in Catalytic Asymmetric Synthesis II (Ed.:, I. Ojima,), Wiley-VCH, New York, 2000, chap. 4, pp 165-189.
206. "Some newer aspects of organozirconium chemistry of relevance to organic synthesis. Zr-catalyzed enantioselective carbometallation":, E. Negishi, Pure Appl. Chem. 2001, 73, 239-242.
207. "Zirconium-catalyzed enantioselective carboalumination of "unactivated" alkenes as a new synthetic tool for asymmetric carbon-carbon bond formation":, E. Negishi, S. Huo, Pure Appl. Chem. 2002, 74, 151-157.
208. "Synthesis and reactivity of zirconocene derivatives":, E. Negishi, S. Huo, in Titanium and Zirconium in Organic Synthesis (Ed.:, I. Marek,), Wiley-VCH, Weinheim, 2002, Chap. 1, 1-49.
209. "Disasteroselective, enantioselective, and regioselective carboalumination reactions catalyzed by zirconocene derivatives":, E. Negishi, Z. Tan, in Topics in Organometallic Chemistry (Ed.:, T. Takahashi,), 2004, Chap. 4, pp 139-176.
210. "A quarter of a century of explorations in organozirconium chemistry":, E. Negishi, Dalton Trans. 2005, 827-848.
211. "Chiral organoalanes and their organic derivatives via zirconium-catalyzed asymmetric carboalumination of terminal alkenes":, E. Negishi, D. Y. Kondakov, 1999, (Purdue Research Foundation) US Patent 6,002,037, Dec. 14, 1999 (Applied Oct. 14, 1997).
212. "(-)-Dichlorobis[(1,2,3,3a,7a-η)-1-[(1S,2S,5R) -5-methyl-2-(1-methyl-ethyl)cyclohexyl-1H-inden-1-yl]zirconium and its (+)-(1R,2R,5S)-isomer":, E. Negishi, S. Huo, In Encyclopedia of Reagents for Organic Synthesis (Ed.:, L. A. Paquette,), Wiley, New York, 2002.
213. E. Negishi, G. Wang, C. T. Lee, S. Xu, unpublished results.