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. Author manuscript; available in PMC: 2012 Jan 21.
Published in final edited form as: Org Lett. 2010 Dec 13;13(2):184–187. doi: 10.1021/ol102567h

Table 2.

Asymmetric synthesis of tertiary benzylic alcohols.a

entry product Mb yield
(%)c 		drd entry product Mb yield
(%)c 		drd
graphic file with name nihms-258484-t0007.jpg graphic file with name nihms-258484-t0008.jpg
1 2a: R = Ph [Ce] 95 >50:1 (~50:1) 15 2o: R = CCPh [Ce] 78 >50:1 (~50:1)
2 2c: R = 2-CH3-Ph [Ce] 88 >50:1 (~50:1) 16 2p: R = CC-(2-Th) [Ce] 82 >50:1 (33:1)
3 2d: R = 6-CH3O-2-Np [Ce] 81 >50:1 (20:1) 17 2q: R = 4-CH3O-Ph MgBr 79 >50:1 (>50:1)
4 2e: R = Si(iPr)3 [Ce] 87 >50:1 (>50:1) 18 2r: R = 2-Propenyl MgBr 72 >50:1 (25:1)
5 2f: R = CH2OTBS [Ce] 65 33:1 (12:1) graphic file with name nihms-258484-t0009.jpg
graphic file with name nihms-258484-t0010.jpg
6 2b: Ar = Ph MgBr 83 >50:1 (~50:1) 19 2s: R = 4-CH3O-Ph MgBr 75 >50:1 (~50:1)
7 2g: Ar = 3,5-(CF3)2-Ph MgBr 82 >50:1 (>50:1) 20 2t: R = 6-CH3O-2-Np MgBr 79 >50:1 (>50:1)
8 2h: Ar =4-CH3O-Ph MgBr 87 >50:1 (>50:1) 21 2u: R = CCPh [Ce] 77 >50:1 (~50:1)
graphic file with name nihms-258484-t0011.jpg graphic file with name nihms-258484-t0012.jpg
9 2i: R = H MgBr 74 >50:1 (>50:1) 22 2v: R1 = H
R2 = R3 = CH3 		MgBr 80) >50:1 (25:1)
10 2j: R = CH3 MgBr 90 >50:1 (33:1) 23 2u: R1 = CH3
R2 = R3 = H		 MgBr 86 >50:1 (20:1)
graphic file with name nihms-258484-t0013.jpg graphic file with name nihms-258484-t0014.jpg
11 2k: R = Ph [Ce] 72 >50:1 (11:1) 24 2x: R = CCPh [Ce] 77 >50:1 (14:1)
12 2l:R = 3,5-(CF3)2-Ph [Ce] 81 >50:1 (14:1) 25 2y: R = Ph MgBr 85 >50:1 (~50:1)
13 2m: R = CH2N(CH3)2 [Ce] 71 >50:1 (~50:1) 26 graphic file with name nihms-258484-t0015.jpg [Ce] 79) >50:1 (10:1)
14 graphic file with name nihms-258484-t0016.jpg MgBr 84 >50:1 (>50:1)
a

Reaction conditions as in Table 1, entry 4 (M = [Ce]) or 6 (M = MgBr) on a 0.4 mmol scale. The (S)-sulfoxides were used.

b

[Ce] = reagent derived from alkynyl Li and CeCl3.

c

Yield of isolated single diastereomer except entry 5 (33:1 dr). The numbers in parenthesis represent conversion of 1 as determined by 1H NMR analysis of crude reaction mixture.

d

dr determined by 1H NMR analysis of purified material. The numbers in parenthesis represent dr of crude reaction products. TBS = tert-butyldimethyl silyl; Tol = p-tolyl; Np = naphthyl; Th = thienyl.