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. Author manuscript; available in PMC: 2006 Jun 14.
Published in final edited form as: Angew Chem Int Ed Engl. 2004 Sep 13;43(36):4788–4791. doi: 10.1002/anie.200460612

Table 1.

Optimization of the rhodium-catalyzed allylic etherification with the copper(I) alkenyl alkoxide derived from (R)-2 (n=1).[a]

graphic file with name nihms-3120-0003.jpg

Entry Catalyst Additive 3/4[b],[c] d.r.3a/3b[b] Yield[%][d]
1 [RhCl(PPh3)3]/P(OMe)3 CuCl 9:1 2:1 20
2 [RhCl(PPh3)3]/P(OMe)3 CuI 11:1 4:1 63
3 [{RhCl(C2H4)2]/P(OMe)3 CuI 13:1 3:1 63
4 [RhCl(PPh3)3]/P(OMe)3 CuI/PPh3 13:1 7:1 46
5 [RhCl(PPh3)3]/P(OMe)3 CuI/P(OMe)3 49:1 ≥99:1 72
6 [RhCl(PPh3)3] CuI/P(OMe)3 24:1 10:1 15
[a]

All reactions (0.25 mmol) were carried out with 10 mol% of the catalyst in tetrahydrofuran with 1.9 equivalents of the copper alkoxide.

[b]

Diastereomeric ratios were determined by capillary GLC on aliquots of the crude reaction mixture.

[c]

Authentic standards were prepared independently by using copper cyanide as an additive.

[d]

Yields of the isolated products. Bn=benzyl, HMDS=hexamethyldisilazide, PMP=p-methoxyphenyl, RT=room temperature.