Homogeneous Metal Salt Catalysis in Organic Reactions. III. The Preparation of Allyl Ethers by Allyl Transfer Reactions^1,2

The importance of polar, resonance, steric and solvent effects in the addition of sulfonyl radicals to alkenes

“…95-97 "C (ethanol) (Found: C, 45.6;H, 5.4;S, 8.2. C15H,,I0,S requires C, 45.93;H, 5.40;S, 8.17%);v(KBr disk)/crn-l 3043, 2921v(KBr disk)/crn-l 3043, , 2879v(KBr disk)/crn-l 3043, , 1600v(KBr disk)/crn-l 3043, , 1464v(KBr disk)/crn-l 3043, , 1448v(KBr disk)/crn-l 3043, , 1303v(KBr disk)/crn-l 3043, , 1141v(KBr disk)/crn-l 3043, , 1086&(CDC1,,200 MHz) 7.82 (d, 2 H, J8.0, Ar), 7.27 (d, 2 H, J8.0, Ar), 4.88 (ddd, 1 H, J6.6,6.5, 1.9, CHI), 3.56(ddd, 1 H, J8.3,6.6, 1.4, CHTs), 2.47 (s, 3 H, CH,Ar) and 2 ' 1644,1595,1463, 1455, 1377, 1298, 1147, 1121, 1084&(CDCl,, 300 MHz) 7.75 (d, 2 H, J 8.2, Ar), 7.3 1 (d, 2 H, J 8.2, Ar) 139 (24), 109 (49, 108 (43), 93 (24), 92 (16), 91 (29), 81 (21), 80 (28), 79 (39, 67 (loo), 65 (31), 55 (40), 53 (21), 41 (45), 38 (27) and 27 (15). (CH,),28.21 (CH,),26.42 (CH,),25.79 (CH,), 25.57 (CH,), 1 -Cyclohexyl-1 -iodo-2-tosylethane (3a).-Alkene 3 and TsI gave ethane 3a as a solid (73%), m.p.…”

Allyl Ether

“…Diallyl ether reacts with various alcohols in the presence of catalytic amounts of Hg(II) salts in a transetherification reaction. 82 Allylation of sulfides to allyldialkyl sulfonium salts was achieved with diallyl ether and TMS triflate, presumably via in situ formation of labile allyl triflate. 83 With the catalyst (Bu 3 P) 2 NiBr 2 , allylation of morpholine was achieved in 75% yield, without formation of any quaternary ammonium salt.…”

Mild and selective etherification of wheat straw lignin and lignin model alcohols by moisture-tolerant zirconium catalysis

“…While methods for the dehydrative etherification of benzylic alcohols have been reported with the use of several different catalytic systems, [17][18][19][20][21][22][23][24][25][26][27][28][29] only a few examples are known of their direct condensation using allyl alcohol as the nucleophile. [30][31][32][33][34][35] The use of Lewis acids as catalysts for direct etherification can be limited due to their sensitivity to the water produced during the transformation. However, some trivalent and tetravalent metal triflates constitute a moisture-tolerant class of Lewis acids that allow for procedures without water removal techniques.…”

“…While methods for the dehydrative etherification of benzylic alcohols have been reported with the use of several different catalytic systems, 17–29 only a few examples are known of their direct condensation using allyl alcohol as the nucleophile. 30–35…”