Terrahedion Vol. 42, No. 19, pi. 5157 to 5254. 1986 -20/86 SS.oO+.CQ Printed in Great Brilain Pcrgamon Joumsls Ltd. TETRAHEDRON REPORT NUMBER 209 RECENT ADVANCES IN ASYMMETRIC SYNTHESIS-IIt zyxwvutsrqpon J. W. APSIMON and T. LEE COLLIER Department of Chemistry, Carleton University, The OttawaCarleton Institute for Graduate Studies and Research in Chemistry, Ottawa, Ontario, Canada KIS 5B6 (Received in USA 10 February 1986) CONTENTS Introduction . . . . . . . . . . . . . . . . . . . . . . . . . 5158 Reductions . . . . . . Chiral metal hydride complexes . . Aluminium . . . . . . Ttialkylaluminium . . Borane reagents . . . Hydroboration. . . . . . Catalytic Processes . . . . . . . Homogeneous asymmetric hydrogenation . Table of ligand classes . . . . . . . Rhodium catalysts . . . . Ruthenium, iridium, nickel and platinum Hydroformylation . . . . . Asymmetric cross-coupling reactions . . . 5197 . . . 5197 . . . . 5200 . . . . 5201 . . . . . . 5203 . . . . 5206 . . . . . 5209 . . . . 5214 . . . . . . . . . . . Alkylations ......... Enamines ......... Aldimines ......... Hydrazones ........ Oxazolines ......... Michael addition ....... Michael addition to nitrooletins . . Enolate addition ....... Cycloaddition Reactions ............... DielsAlder .................. Chiral dienophile or enophile ............ Chiral dienes ................. Ene reactions ................. 1,3-Dipolar cycloaddition reactions. .......... [3 + 21 Cycloadditions .............. Asymmetric induction catalyzed by external chiral functionahties . . . . . . . . . . . . . Rearrangements . . . . . . . . . ............. 5235 [3,3]- and [2,3]-sigmatropic rearrangements ............. 5235 [2,3]-Sigmatropic rearrangements . . . ............. 5238 . . . 5219 . . . 5219 . . . . . 5219 . . . . 5221 . . . . . 5223 . . . . 5223 . . 5223 . 5224 Epoxidations . . . . . . . . . . . . . . . . . 5228 Sulfur Reagents . . . . . . . . . . . . . . . . . 5232 . . . . . . . . . . . . . . . Addendum. . . . . . . . . 5248 Reductions. . . . . . . . . . . . . . 5240 Hydroboration . . . . . . . . . . . 5242 Alkylation . . . . . . . . . . . . . 5242 DieLAlder . . . . . . . . . . . . . . . . 5245 [2+ 2lCycloadditions . . . . . . . . . . . . . 5246 [2,3]-Sigmatropic rearrangements . . . . . . . . . 5246 . . . . . . . . 5158 5158 5158 5164 5165 5171 5173 5173 5173 5178 5186 5190 5194 Aldol . . . . . . . . . . . . . . 5249 Conclusion . . . . . . . . . . . . . . . . . . . . . . 5249 References. . . . . . . . . . . . . . . . . . . . . . . 5250 f This report extends the coverage of the original report by J. W. ApSimon and R. P. Seguin, “Recent Advances in Asymmetric Synthesis”, Tetrahedron 35, 2797 (1979). 5157