with dichloromethane. The combined organic fraction was dried over anhydrous sodium sulfate and concentrated in vacuo to give a white crystalline powder, which was chromatographed (ThLC), eluting with ethyl acetate-cyclohexane (1:1) to afford the two major products.Fraction A gave the syn 2:2 macrocycle 4, as white crystals:

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of the di product is formed in an S^AE)*®1® reaction of the d2 starting material, and the rest (22.4 -11.7 = 10.7%) is formed in an SN(AE)ipeo reaction of dx starting material. So from 66.1% of dx product, 10.7% undergoes an SN-(AE)ip®°reaction, and the rest (66.1 -10.7 = 55.4%) undergoes an SnÍAE)1®1® reaction, or in other words k/kD = 10.7/55.4 = 0.18. From kH/kO and fe/feD, k^/k can be calculated. kH/k is the ratio of the reaction rate of the Sn(AE)*®1® reaction in the undeuterated compound and the rate of the SN(AE)ip®°r eaction.

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combined acidic layers until it was strongly basic. The basic mixture was extracted with CHzClz (5 X 150 mL), and the combined extracts were dried over Na2S04 and concentrated to produce 0.181 g (66%) of a gummy tan solid. Purification by sublimation (90 "C, 2 mm) gave 1 as a waxy white solid; mp 224-227 OC (sealed tube) (lit.4 mp 265-268 "C). Resublimation produced no significant change in melting point. NMR (CDC13) 6 1.5-2.2 (12 H, m), 2.45-2.75 (1 H, br s, exch), 2.90-3.25 (2 H, br s, NCH); M + found, m / e 137.1208 (calcd for C9H15N, m / e 137.1206).N-Methyl-2-azaadamantane-anti-4,8-diol(2b). Treatment of 0.980 g (6.4 mmol) of 12 with CH3NH2 using the reaction conditions for 2a produced 1.06 g (90%) of 2b after recrystallization from acetonitrile: mp 198-201.5 "C; IR (Nujol) 3362 cm-'; NMR (D20 + DCl) 6 (DSS) 4.30 (1 H, m, CHOH), 4.10 (1 H, m, CHOH), 3.43 (2 H, m, CHN), 3.02 (3 H, s, CH,), 1.56-2.40 (8 H, m); M+ found, m / e 183.1258 (calcd for Cl&Il7NO2, m / e 183.1260). N-Ethyl-2-azaadamantane-anti-4,8-diol (2c). Treatment of 0.50 g (3.29 mmol) of 12 with EtNHz using the reaction conditions for 2a produced 0.446 g (69%) of 2c after recrystallization from acetonitrile: mp 178-179 OC; IR (Nujol) 3338 cm-'; NMR (D20) 6 (DSS) 1.01 (3 H, t, CHJ, 1.5-2.6 (8 H, m), 2.75 (4 H, m, NCH), 3.95 (2 H, s, CHOH); M+ found, m / e 197.1414 (calcd for ClIHldO2, m / e 197.1417). N-Isopropyl-2-azaadamantane-an ti-4,8-diol(2d). A solution of 1.00 g (6.58 mmol) of 12 and 1.94 (2.39 mmol) of isopropylamine in 14 mL MeOH was heated at 130 "C in a steel bomb for 24 h. After the solution was cooled, the solvent was evaporated and the residue recrystallized from acetonitrile to produce 0.869 g (63%) of 2 d mp 169-172 "C; IR (Nujol) 3284 cm-'; NMR (DzO + DC1) 6 (DSS) 1.38 (6 H, dd, CH3) 1.6-2.6 (8 H, m), 3.55-4.35 (5 H, m, CHNH, CHOH); M+ found, m / e 211.1567 (calcd for ClzHzlNOz, m / e 211.1573). N-Isoamyl-2-azaadamantane-anti-4,8-diol(2e). Treatment of 1.00 g (6.58 mmol) of 12 with 2.87 g (32.9 "01) of isoamylamine using the reaction conditions for 2d produced 1.058 g (67%) of 2e after recrystallization from acetonitrile: mp 113-116.5 "C; IR (Nujol) 3320 cm-I; NMR (DzO + DCl) 6 (DSS) 0.92 (6 H, d, CHJ, 1.4-2.4 (11 H, m), 3.20-3.67 (4 H, m, CHN), 4.12 (1 H, m, CHOH), 4.28 (1 H, m, CHOH); M+ found, m / e 239.1874 (calcd for C14-H25NO2, m / e 239.1886). N-Benzyl-2-azaadamantane-anti-4,8-diol (2f). Treatment of 1.00 g (6.58 "01) of 12 with 3.52 g (33.0 mmol) freshly distilled benzylamine using the reaction conditions for 2d produced 1.157 g (68%) of 2f after recrystallization from benzene: mp 121-123.5 "C; IR (Nujol) 3440 cm-'; NMR (DzO + DC1) 6 (DSS) 1.75-2.42 (8 H, m, ring CHz, CH), 3.43, 3.49 (2 H, br d, CHN), 4.15 (1 H, m, CHOH), 4.54-4.70 (3 H, m, CHOH, CHzPh), 7.54 (5 H, s, Ph); M+ found m / e 259.1566 (calcd for C16HzlN02, m / e 259.1573). N-Phenyl-2-azaadamantane-anti-4,8-diol(2g). To a stirred solution of 0.400 g (2.63 mmmol) of 12 dissolved in 5 mL of trifluoroethanol under Nz was added 0.270 g (2.89 mmol) of freshly distille...