Tetrahedron report number 721 Palladium-catalysed reactions of alcohols. Part C: Formation of ether linkages * Jacques Muzart * Unite ´ Mixte de Recherche ‘Re ´actions Se ´lectives et Applications’, CNRS, Universite ´ de Reims Champagne-Ardenne, B.P. 1039, 51687 Reims Cedex 2, France Received 17 March 2005 Contents 1. Introduction .................................................................. 5956 2. Addition of alcohols to h 3 -allylpalladium intermediates .................................. 5956 2.1. h 3 -Allylpalladium intermediates from allylic alcohols .............................. 5956 2.1.1. Intermolecular reactions .............................................. 5956 2.1.2. Intramolecular reactions .............................................. 5957 2.2. h 3 -Allylpalladium intermediates from allylic alcohol derivatives ...................... 5957 2.2.1. Intermolecular reactions .............................................. 5957 2.2.2. Intramolecular reactions .............................................. 5959 2.3. h 3 -Allylpalladium intermediates from vinyl epoxides ............................... 5960 2.4. h 3 -Allylpalladium intermediates from alkylidene cyclopropanes ....................... 5960 2.5. h 3 -Allylpalladium intermediates from allylic chlorides .............................. 5962 2.6. h 3 -Allylpalladium intermediates from allylsilanes ................................. 5962 2.7. h 3 -Allylpalladium intermediates from alkenes .................................... 5963 2.8. h 3 -Allylpalladium intermediates from 1,2-dienes .................................. 5963 2.8.1. From allenes ...................................................... 5963 2.8.2. From allenols ...................................................... 5963 2.9. h 3 -Allylpalladium intermediates from 1,3-dienes .................................. 5964 2.9.1. Intermolecular reactions .............................................. 5964 2.9.2. Intramolecular reactions .............................................. 5966 2.10. h 3 -Allylpalladium intermediates from alkynes .................................... 5967 3. Oxypalladation of unsaturated carbon–carbon bonds .................................... 5968 3.1. Oxypalladation of alkenes ................................................... 5968 3.1.1. Intermolecular addition of alcohols to alkenes .............................. 5969 3.1.2. Intramolecular reactions of alkenols ..................................... 5970 3.1.3. Intramolecular reactions of alkenediols ................................... 5975 3.2. Oxypalladation of vinyl ethers ............................................... 5976 3.3. Oxypalladation of cumulenes ................................................ 5977 0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.tet.2005.04.002 Tetrahedron 61 (2005) 5955–6008 * See Refs. 1 and 2. Keywords: Palladium; Alcohols; Etherification; Heterocyclisation; Oxypalladation; h 3 -Allylpalladium. Abbreviations: atm, atmosphere; BINAP, 2,2 0 -bis(diphenylphosphino)-1,1 0 -binaphthyl; cat., catalytic; COD, 1,5-cyclooctadiene; conv, conversion; Cy, cyclohexyl; dba, dibenzylidene acetone; DBU, 1,8-diazabicyclo[5.4.0]undec-7ene; de, diastereoisomeric excess; DMA, N,N-dimethylacetamide; dppe, 1,2- bis(diphenylphosphino)ethane; dppb, 1,4-bis(diphenylphosphino)butane; dppf, 1,1 0 -bis(diphenylphosphino)ferrocene; dppp, 1,3-bis(diphenylphosphino)pro- pane; dr, diastereoisomeric ratio; ee, enantiomeric excess; equiv, equivalent; MS, molecular sieves; phenan, phenanthroline; Py, pyridine; rt, room temperature; THP, tetrahydropyranyl; tol-BINAP, 2,2 0 -bis(di-p-tolylphosphino)-1,1 0 -binaphthyl; Ts, 4-methylphenylsulfonyl; TON, turnover number; TPPTS, tris(3-sulfanatophenylphosphine) trisodium. * Tel.: C33 3 2691 3237; fax: C33 3 2691 3166; e-mail: jacques.muzart@univ-reims.fr