Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007

Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 6945 Weinheim, 2007

A New Method for Constructing Quaternary Carbon Centres: Tandem Rhodium-Catalysed,4-Addition/Intramolecular Cyclization. Jérôme Le Nôtre, David van Mele, Christopher G. Frost * Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK Fax: (+44) 225 38642, e-mail: c.g.frost@bath.ac.uk Supporting Information Characterisation of products Dimethyl 2-benzylsuccinate (3): [] The reaction was performed following the general procedure with TMSCl on mmol scale. After purification, the, -alkene (3) was obtained as a white solid (222 mg, 94% yield). H NMR (300 MHz, CDCl 3 ): δ 7.24-7.03 (m, 5 H), 3.59 (s, 3 H), 3.56 (s, 3 H), 3.-2.94 (m, 2 H), 2.70-2.55 (m, 2 H), 2.32 (dd, J = 6.9, 4.8 Hz, H); 3 C NMR (75 MHz, CDCl 3 ): δ 74.4, 72.0, 37.9, 28.7, 28.3, 26.4, 5.6, 5.5, 42.9, 37.5, 34.6; MS (EI): m/z 236 ([M + ], 5), 76 (50), 63 (25), 45 (25), 3 (50), 7 (95), 5 (40), 03 (5), 9 (00), 77 (5), 65 (35), 59 (25); HRMS (EI): calculated for C 3 H 6 4 [M+H] + 237.2, found 237.22.

Dimethyl dicarboxylate (4): -benzyl-3-(2-methoxy-2-oxoethyl)-4-oxocyclopentane-,3- C 2 Me C 2 Me C 2 Me The reaction was performed following the general procedure without TMSCl on 0.5 mmol scale. After purification, the cyclic ketone (4) was obtained as a pale yellow oil (0. mg, 0% yield). H NMR (300 MHz, CDCl 3 ): δ 7.28-7.3 (m, 3 H), 7.-6.98 (m, 2 H), 3.69 (s, 3 H), 3.68 (s, 3 H), 3.66 (s, 3 H), 3.55-3.32 (m, H), 3.2-2.76 (m, 5 H), 2.6-2.36 (m, 2 H); 3 C NMR (75 MHz, CDCl 3 ): δ 209.0, 75.7, 70.8, 70., 36.3, 29.4, 28.2, 26.9, 58.0, 52.6, 52.0, 5.7, 48.9, 46.2, 44.2, 4.0, 37.; MS (EI): m/z 362 ([M + ], 3), 330 (5), 27 (0), 204 (0), 76 (20), 44 (0), 27 (20), 7 (20), 6 (25), 5 (30), 9 (00), 77 (0), 65 (5), 59 (30). Dimethyl 2-methylenepentanedioate (8): [2] The reaction was performed following either the method A on 5 mmol scale, or the method B on 20 mmol of trimethyl phosphonoacetate. After purification, the, - alkene (8) was obtained as a colourless oil (Method A: 362 mg, 42% yield; Method B: 992 mg, 29% yield). H NMR (300 MHz, CDCl 3 ): δ 6.2 (br s, H), 5.53 (br s, H), 3.70 (s, 3H), 3.60 (s, 3H), 2.63-2.5 (m, 2H), 2.50-2.39 (m, 2H); 3 C NMR (75 MHz, CDCl 3 ): δ 72.9, 66.9, 38.6, 25.8, 5.7, 5.4, 32.7, 27.2. MS (EI): m/z 72 ([M + ], ), 40 (20), 2 (40), 8 (20), 7 (0), 59 (00), 53 (80); HRMS (EI): calculated for C 8 H 2 4 [M+H] + 73.0808, found 73.080. Dimethyl 2-methylenehexanedioate (9): [3] The reaction was performed following either the method A on 50 mmol scale, or the method B on 20 mmol of trimethyl phosphonoacetate. After purification, the, - 2

alkene (9) was obtained as a colourless oil (Method A: 4.7 g, 50% yield; Method B: 70 mg, 25% yield). H NMR (300 MHz, CDCl 3 ): δ 6.3 (br s, H), 5.50 (br s, H), 3.7 (s, 3H), 3.6 (s, 3H), 2.28 (t, J = 6.9 Hz, 4H),.77 (quintet, J = 6.9 Hz, 2H); 3 C NMR (75 MHz, CDCl 3 ): δ 73.6, 67.3, 39.5, 25.2, 5.7, 5.3, 33.2, 3., 23.4; MS (EI): m/z 86 ([M + ], ), 54 (90), 26 (00), (50), 95 (75), 84 (60), 74 (25), 67 (80), 59 (80), 55 (55); HRMS (EI): calculated for C 9 H 4 4 [M+NH 4 ] + 204.230, found 204.23. -tert-butyl 6-methyl 2-methylenehexanedioate (0): The reaction was performed following the method A on 7 mmol scale. After purification, the, -alkene (0) was obtained as a colourless oil (.7 g, 43% yield). H NMR (300 MHz, CDCl 3 ): δ 6.00 (br s, H), 5.40 (br s, H), 3.60 (s, 3H), 2.26 (t, J = 7.5 Hz, 2H), 2.23 (t, J = 7.5 Hz, 2H),.74 (quintet, J = 7.5 Hz, 2H),.42 (s, 9H); 3 C NMR (75 MHz, CDCl 3 ): δ 73.8, 66.2, 4.3, 24.2, 80.5, 5.8, 5.4, 33.4, 3.2, 28.8, 28.4, 28.0, 23.6; MS (EI): m/z 228 ([M + ], 0), 72 (0), 54 (5), 4 (0), 23 (0), 95 (0), 67 (0), 57 (00); HRMS (EI): calculated for C 2 H 20 4 [M+NH 4 ] + 246.700, found 246.700. Methyl 2-methylene-6-oxo-6-(pyrrolidin--yl)hexanoate (): N The reaction was performed following the method A on 50 mmol scale. After purification by flash column chromatography eluting ethyl acetate/petroleum ether (2/), the, -alkene () was obtained as a colourless oil (6.6 g, 59% yield). H NMR (300 MHz, CDCl 3 ): δ 6.4 (br s, H), 5.56 (br s, H), 3.72 (s, 3H), 3.43 (t, J = 6.9 Hz, 2H), 3.37 (t, J = 6.9 Hz, 2H), 2.34 (t, J = 7.5 Hz, 2H), 2.26 (t, J = 7.5 Hz, 2H),.92 (app t, J = 6.6 Hz, 2H),.89-.69 (m, 4H); 3 C NMR (75 MHz, CDCl 3 ): δ 7.0, 67.6, 40.0, 25.0, 5.7, 46.4, 45.5, 33.9, 3.3, 26.0, 24.3, 23.3; MS (EI): m/z 225 3

([M + ], 0), 225 (0), 94 (0), 66 (0), 26 (0), 3 (00), 98 (30), 70 (60), 55 (40); HRMS (EI): calculated for C 2 H 9 N 3 [M+H] + 226.438, found 226.437. Dimethyl 2-methyleneheptanedioate (2): [4] The reaction was performed following the method A on 25 mmol scale. After purification, the, -alkene (2) was obtained as a colourless oil (.9 g, 38% yield). H NMR (300 MHz, CDCl 3 ): δ 6.4 (br s, H), 5.54 (br s, H), 3.74 (s, 3H), 3.66 (s, 3H), 2.33 (t, J = 7.8 Hz, 2H), 2.3 (t, J = 7.5 Hz, 2H),.65 (quintet, J = 7.8 Hz, 2H),.49 (quintet, J = 7.8 Hz, 2H); 3 C NMR (75 MHz, CDCl 3 ): δ 74.0, 67.6, 40., 24.9, 5.8, 5.5, 33.8, 3.5, 27.7, 24.4; MS (EI): m/z 200 ([M + ], 0), 200 ([M] + <), 69 (0), 40 (20), 36 (0), 27 (0), 08 (30), 98 (0), 95 (30), 8 (80), 74 (20), 67 (50), 59 (00), 55 (30); HRMS (EI): calculated for C 0 H 6 4 [M+NH 4 ] + 28.387, found 28.389. -tert-butyl 7-methyl 2-methyleneheptanedioate (3): The reaction was performed following the method A on 25 mmol scale. After purification, the, -alkene (3) was obtained as a colourless oil (2.3 g, 36% yield). H NMR (300 MHz, CDCl 3 ): δ 6.02 (br s, H,), 5.42 (br s, H,), 3.64 (s, 3H), 2.3 (t, J = 7.5 Hz, 2H), 2.25 (t, J = 7.5 Hz, 2H),.64 (quintet, J = 7.5 Hz, 2H),.52.42 (m, 2H),.47 (s, 9H); 3 C NMR (75 MHz, CDCl 3 ): δ 73.9, 66.4, 4.9, 23.6, 80.4, 5.4, 33.8, 3.5, 28.0, 27.9, 24.5; MS (EI): m/z 242 ([M + ], 0), 68 (0), 55 (0), 40 (0), 09 (0), 8 (20), 67 (20), 57 (00); HRMS (EI): calculated for C 3 H 22 4 [M+H] + 243.59, found 243.593. Isopropyl 4-bromobutanoate (5a): [5] Br 4

The esterification of 4-bromobutyric acid was performed following classical experimental procedure. 4-bromobutyric acid (4.8 g, 25 mmol) was stirred at room temperature for 48 h in dry isopropanol (25 ml) in the presence of a catalytic amount of concentrated sulfuric acid (0. ml). After evaporation of the solvent, the crude was extracted with ethyl acetate, washed twice with a saturated sodium hydrogenocarbonate solution, then with water and finally with brine. The solution was dried over MgS 4, filtered and evaporated under vacuum to afford the isopropyl 4- bromobutanoate (5a) (3.55 g, 68% yield) as colourless oil which was use without any further purification. H NMR (300 MHz, CDCl 3 ): δ 4.98 (heptet, J = 6.0 Hz, H), 3.40 (t, J = 6.0 Hz, 2H), 2.40 (t, J = 6.9 Hz, 2H), 2.0 (quintet, J = 6.9 Hz, 2H),.5 (d, J = 6.0 Hz, 6H); 3 C NMR (75 MHz, CDCl 3 ): δ 7.9, 67.8, 32.8, 27.8, 2.7. Methyl 6-bromohexanoate (5b): [6] Br The reaction was performed following the procedure described above with 6- bromohexanoic acid (9.75 g, 50 mmol) in 50 ml of dry methanol. Methyl 6- bromohexanoate (5b) (8.59 g, 82 % yield) was then obtained as a colourless oil. H NMR (300 MHz, CDCl 3 ): δ 3.65, (s, 3H), 3.39 (t, J = 6.0 Hz, 2H), 2.30 (t, J = 6.9 Hz, 2H), 2.85 (quintet, J = 6.7 Hz, 2H), 2.60 (quintet, J = 6.7 Hz, 2H), 2.45 (quintet, J = 6.7 Hz, 2H); 3 C NMR (75 MHz, CDCl 3 ): δ 73.8, 5.4, 33.7, 33.3, 32.6, 27.5, 23.9. tert-butyl 4-bromobutanoate (5c): [7] Br Concentrated sulfuric acid (0.2 ml) was added to a solution of 4-bromobutyric acid (3.34 g, 20 mmol), tert-butanol (9.2 ml, 0. mol), magnesium sulfate (9.6 g, 80 mmol) in dry dichloromethane (80 ml). The reaction mixture was vigorously stirred for 48 h at room temperature. The reaction was then quenched with a saturated sodium bicarbonate solution. The organic layer was separated, washed with water, dried over MgS 4, and evaporated to dryness. The crude was then purified by column chromatography using dichloromethane as eluent to afford tert-butyl 4- bromobutanoate (5c) (.3 g, 30% yield). H NMR (300 MHz, CDCl 3 ): δ 3.40 (t, J = 5

6.7 Hz, 2H), 2.34 (t, J = 7. Hz, 2H), 2.0 (quintet, J = 6.7 Hz, 2H),.35 (s, 9H); 3 C NMR (75 MHz, CDCl 3 ): δ 7.8, 80.4, 33.6, 32.6, 27.9, 27.8. Benzyl 4-bromobutanoate (5d): [8] Br The reaction was performed following the procedure described above using 4- bromobutyric acid (3.34 g, 20 mmol), concentrated sulfuric acid (0.2 ml), magnesium sulfate (9.6 g, 80 mmol) and benzyl alcohol (0.4 ml, 0. mol) in 80 ml of dry dichloromethane. After purification by column chromatography (CH 2 Cl 2 ), benzyl 4- bromobutanoate (5d) (4.89 g, 95% yield) was obtained as a colourless oil. H NMR (300 MHz, CDCl 3 ): δ 7.46-7.30 (m, 5H), 5.4 (s, 2H), 3.53 (t, J = 6.5 Hz, 2H), 2.59 (t, J = 7.0 Hz, 2H), 2.20 (quintet, J = 7.0 Hz, 2H); 3 C NMR (75 MHz, CDCl 3 ): δ 72.2, 35.7, 28.5, 28.3, 28.2, 66.3, 32.6, 32.4, 27.6. 6-Ethyl -methyl 2-methylenehexanedioate (7): The reaction was performed following the method B on 5 mmol of trimethyl phosphonoacetate. After purification, the, -alkene (7) was obtained as a colourless oil (264 mg, 26% yield). H NMR (300 MHz, CDCl 3 ): δ 6.3 (br s, H), 5.5 (br s, H), 4.08 (q, J = 7.0 Hz, 2H), 3.7 (s, 3H), 2.29 (t, J = 6.9 Hz, 4H),.79 (quintet, J = 6.9 Hz, 2H),.2 (t, J = 7.0 Hz, 3H); 3 C NMR (75 MHz, CDCl 3 ): δ 73.2, 67.3, 39.5, 25.3, 60.2, 5.7, 33.4, 3., 23.4, 4.; MS (EI): m/z 200 ([M + ], ), 68 (5), 55 (20), 54 (20), 40 (25), 26 (30), 2 (20), 95 (30), 8 (0), 67 (40), 59 (00); HRMS (EI): calculated for C 0 H 6 4 [M+H] + 20.2, found 20.22. 6-Isopropyl -methyl 2-methylenehexanedioate (8): 6

The reaction was performed following the method B on 5 mmol of trimethyl phosphonoacetate. After purification, the, -alkene (8) was obtained as a colourless oil (30 mg, 29% yield). H NMR (300 MHz, CDCl 3 ): δ 6.2 (br s, H), 5.50 (br s, H), 4.93 (heptet, J = 6.0 Hz, H), 3.70 (s, 3H), 2.30 (t, J = 6.0 Hz, 2H), 2.2 (t, J = 6.9 Hz, 2H),.73 (quintet, J = 6.9 Hz, 2H),.4 (d, J = 6.0 Hz, 6H); 3 C NMR (75 MHz, CDCl 3 ): δ 72.8, 67.4, 39.7, 25.4, 67.6, 5.8, 33.9, 3.2, 23.6, 2.8; MS (EI): m/z 24 ([M + ], ), 55 (0), 54 (0), 40 (0), 26 (0), 2 (0), 95 (5), 67 (25), 59 (00); HRMS (EI): calculated for C H 8 4 [M+H] + 25.278, found 25.279. 6-tert-Butyl -methyl 2-methylenehexanedioate (9): The reaction was performed following the method B on 2 mmol of trimethyl phosphonoacetate. After purification, the, -alkene (9) was obtained as a colourless oil (222 mg, 48% yield). H NMR (300 MHz, CDCl 3 ): δ 6.2 (br s, H), 5.50 (br s, H), 3.70 (s, 3H), 2.25 (t, J = 6.7 Hz, 2H), 2.5 (t, J = 7. Hz, 2H),.70 (quintet, J = 7. Hz, 2H),.37 (s, 9H); 3 C NMR (75 MHz, CDCl 3 ): δ 72.7, 67.5, 39.8, 25.3, 80., 5.8, 34.8, 3., 28., 23.7; MS (EI): m/z 228 ([M + ], ), 55 (5), 54 (0), 23 (5), 2 (0), 95 (0), 67 (20), 59 (60), 57 (00); HRMS (EI): calculated for C 2 H 20 4 [M+H] + 229.434, found 229.435. 6-Benzyl -methyl 2-methylenehexanedioate (20): The reaction was performed following the method B on 0 mmol of trimethyl phosphonoacetate. After purification, the, -alkene (20) was obtained as a colourless oil (.29 g, 49% yield). H NMR (300 MHz, CDCl 3 ): δ 7.40-7.24 (m, 5H), 7

6. (br s, H), 5.48 (br s, H), 5.06 (s, 2H), 3.68 (s, 3H), 2.35-2.20 (m, 4H),.73 (quintet, J = 6.9 Hz, 2H); 3 C NMR (75 MHz, CDCl 3 ): δ 73.0, 67.3, 39.4, 35.9, 28.4, 28.3, 28.2, 28., 25.4, 66., 5.7, 33.4, 3., 23.4; MS (EI): m/z 262 ([M + ], ), 55 (0), 24 (0), 07 (0), 9 (00), 77 (5), 65 (20), 59 (5), 5 (0); HRMS (EI): calculated for C 5 H 8 4 [M+H] + 263.278, found 263.279. Dimethyl 2-methyleneoctanedioate (2): The reaction was performed following the method B on 5 mmol of trimethyl phosphonoacetate. After purification, the, -alkene (2) was obtained as a colourless oil (27 mg, 24% yield). H NMR (300 MHz, CDCl 3 ): δ 6.2 (br s, H), 5.50 (br s, H), 3.7 (s, 3H), 3.62 (s, 3H), 2.29-2.9 (m, 4H),.60 (quintet, J = 6.9 Hz, 2H),.40 (quintet, J = 6.9 Hz, 2H),.27 (quintet, J = 6.9 Hz, 2H); 3 C NMR (75 MHz, CDCl 3 ): δ 74., 67.7, 40.5, 24.6, 5.7, 5.4, 33.9, 3.6, 28.6, 28.0, 24.6; MS (EI): m/z 24 ([M + ], ), 54 (20), 50 (30), 22 (30), 09 (0), 95 (35), 8 (25), 74 (0), 67 (30), 59 (00); HRMS (EI): calculated for C H 8 4 [M+NH 4 ] + 232.543, found 232.542. Dimethyl 2-benzylpentanedioate (22a): [9] The reaction was performed following the general procedure on 0.5 mmol of, - alkene. After purification, the,4-addition product (22a) was obtained as a pale yellow oil (6 mg, 93% yield). H NMR (300 MHz, CDCl 3 ): δ 7.4-6.92 (m, 5H), 3.45 (s, 3H), 3.40 (s, 3H), 2.8-2.70 (m, H), 2.60-2.47 (m, 2H), 2.2-2.05 (m, 2H),.8-.62 (m, 2H); 3 C NMR (75 MHz, CDCl 3 ): δ 75., 73., 38.6, 28.7, 28.3, 26.4, 5.5, 46.5, 38.2, 3.6, 26.6; MS (EI): m/z 250 ([M + ], 5), 90 (60), 87 (25), 59 (20), 3(30), 30 (00), 7 (60), 5 (20), 03 (0), 9 (95), 77 (0), 65 (25), 59 (5); HRMS (EI): calculated for C 7 H 24 4 [M+NH 4 ] + 268.543, found 268.54. 8

Dimethyl 2-benzyloctanedioate (25a): The reaction was performed following the general procedure on 0.5 mmol of, - alkene. After purification, the,4-addition product (25a) was obtained as a colourless oil (32 mg, 90% yield). H NMR (300 MHz, CDCl 3 ): δ 7.8-6.95 (m, 5H), 3.5 (s, 3H), 3.44 (s, 3H), 2.8-2.75 (m, H), 2.60-2.40 (m, 2H), 2.2 (t, J = 6.9 Hz, 2H),.59-.30 (m, 4H),.22-.08 (m, 4H); 3 C NMR (75 MHz, CDCl 3 ): δ 76.0, 74., 39.3, 28.7, 28.3, 26.3, 5.4, 5.3, 38.5, 33.9, 3.8, 28.9, 28.0, 27.0, 24.7; MS (EI): m/z 292 ([M + ], 3), 232 (20), 200 (0), 3 (25), 7 (30), 04 (20), 9 (00), 77 (0), 65 (5), 59 (35); HRMS (EI): calculated for C 7 H 24 4 [M+NH 4 ] + 30.203, found 30.204. Reaction using dimethyl 2-methylenehexanedioate (9) (93 mg, 0.5 mmol) as starting, -alkene: Methyl -benzyl-2-oxocyclopentanecarboxylate (23a): [0] cyclic product (23a) was obtained as a colourless oil (89 mg, 77% yield). H NMR (300 MHz, CDCl 3 ): δ 7.23-7. (m, 3H), 7.08-6.99 (m, 2H), 3.64 (s, 3H), 3.4, 3.02 (2 x d(ab), J = 4.0 Hz, 2H), 2.4-2.22 (m, 2H), 2.0 (t, H, J = 6.7 Hz),.95-.72 (m, 2H),.60-.45 (m, H); 3 C NMR (75 MHz, CDCl 3 ): δ 24.8, 7.3, 36.4, 30.0, 28.7, 28.3, 26.8, 6.4, 52.6, 39.0, 38.3, 3.6, 9.4; MS (EI): m/z 232 ([M + ], 5), 24 (20), 73 (30), 72 (25), 55 (5), 45 (30), 44 (25), 3 (20), 30 (55), 9

29 (35), 28 (20), 7 (50), 6 (40), 5 (70), 9 (00), 77 (25), 65 (50), 59 (30); HRMS (EI): calculated for C 4 H 6 3 [M+NH 4 ] + 250.438, found 250.439. Methyl -(4-fluorobenzyl)-2-oxocyclopentanecarboxylate (23b): [] F cyclic product (23b) was obtained as a colourless oil (3 mg, 90% yield). H NMR (300 MHz, CDCl 3 ): δ 7.-7.02 (m, 2H), 6.92 (tm, J = 9.0 Hz, 2H), 3.68 (s, 3H), 3.0, 3.00 (2 x d(ab), J = 4.0 Hz, 2H), 2.45-2.30 (m, 2H), 2.-.80 (m, 3H),.66-.55 (m, H); 3 C NMR (75 MHz, CDCl 3 ): δ 25.5, 72., 62.7 (d, J = 245.4 Hz), 33. (d, J = 3.0 Hz), 32.5 (d, J = 6.8 Hz), 6. (d, J = 2. Hz), 6.4, 52.7, 38.3, 38.2, 3.7, 9.4; MS (EI): m/z 250 ([M + ], 5), 222 (0), 9 (20), 90 (5), 89 (0), 63 (0), 49 (0), 48 (40), 47 (20), 46 (0), 35 (30), 34 (25), 33 (50), 5 (20), 0 (0), 09 (00), 96 (0), 84 (0), 83 (20), 59 (0); HRMS (EI): calculated for C 5 H 4 F 3 [M+NH 4 ] + 268.343, found 268.345. Methyl -( naphthalen--ylmethyl)-2-oxocyclopentanecarboxylate (23c): cyclic product (23c) was obtained as a colourless oil (23 mg, 87% yield). H NMR (300 MHz, CDCl 3 ): δ 7.96 (d, J = 8.4 Hz, H), 7.77 (d, J = 8.4 Hz, H), 7.66 (d, J = 8.4 Hz, H), 7.42 (quintet x m, J = 8.4 Hz, 2H), 7.25 (t, J = 8.4 Hz, H), 7.9 (d,, J = 8.4 Hz, H), 3.79, 3.50 (2 x d(ab), J = 4.0 Hz, 2H), 3.65 (s, 3H), 2.40-2.2 (m, 2H),.90-.59 (m, 3H),.44-.34 (m, H); 3 C NMR (75 MHz, CDCl 3 ): δ 25.2, 7.8,

33.7, 33.0, 32.9, 28.7, 28.4, 28.0, 27.6, 26.0, 25.3, 24.0, 6.8, 52.7, 38., 33.3, 32., 9.4; MS (EI): m/z 282 ([M + ], 0), 205 (5), 65 (40), 52 (20), 4 (00), 28 (30), 5 (35), 59 (20); HRMS (EI): calculated for C 8 H 8 3 [M+NH 4 ] + 300.594, found 300.595. Methyl -(3-methylbenzyl)-2-oxocyclopentanecarboxylate (23d): [2] cyclic product (23d) was obtained as a colourless oil (3 mg, 92% yield). H NMR (300 MHz, CDCl 3 ): δ 7.-7.04 (m, H), 6.99-6.92 (m, H), 6.89-6.80 (m, 2H), 3.65 (s, 3H), 3.0, 2.99 (2 x d(ab), J = 4.0 Hz, 2H), 2.40-2.20 (m, 2H), 2.23 (s, 3H), 2.03-.72 (m, 3H),.6-.48 (m, H); 3 C NMR (75 MHz, CDCl 3 ): δ 24.9, 7.4, 37.9, 36.4, 30.9, 28.3, 27.6, 27., 6.5, 52.6, 39.0, 38.4, 3.6, 2.4, 9.4; MS (EI): m/z 246 ([M + ], 0), 228 (50), 87 (35), 86 (20), 7 (55), 69 (20), 59 (35), 58 (25), 45 (20), 44 (45), 43 (35), 3 (50), 30 (45), 29 (60), 28 (45), 27 (20), 6 (35), 5 (70), 06 (5), 05 (00), 92 (20), 9 (50), 77 (30), 59 (20); HRMS (EI): calculated for C 5 H 8 3 [M+NH 4 ] + 264.594, found 264.593. Methyl -(3,5-dimethylbenzyl)-2-oxocyclopentanecarboxylate (23e): cyclic product (23e) was obtained as a colourless oil ( mg, 85% yield). H NMR (300 MHz, CDCl 3 ): δ 6.79 (br s, H), 6.64 (br s, 2H), 3.62 (s, 3H), 3.05, 2.95 (2 x d(ab), J = 4.0 Hz, 2H), 2.40-2.22 (m, 2H), 2.8 (s, 6H), 2.04-.72 (m, 3H),.6-.4 (m, H); 3 C NMR (75 MHz, CDCl 3 ): δ 24.9, 7.4, 37.7, 36.3, 28.4,

27.9, 6.4, 53.4, 52.5, 38.9, 38.3, 3.5, 2.2, 9.4; MS (EI): m/z 260 ([M + ], 5), 242 (30), 85 (30), 73 (20), 44 (20), 43 (20), 30 (0), 29 (30), 28 (30), 20 (0), 9 (00), 06 (5), 05 (20), 9 (30), 77 (20), 59 (0); HRMS (EI): calculated for C 6 H 20 3 [M+NH 4 ] + 278.75, found 278.752. Methyl -(2,6-dimethoxybenzyl)-2-oxocyclopentanecarboxylate (23f): Me Me cyclic product (23f) was obtained as a colourless oil (0 mg, 75% yield). H NMR (300 MHz, CDCl 3 ): δ 7.0 (t, J = 8.5 Hz, H), 6.42 (d, J = 8.5 Hz, 2H), 3.65 (s, 6H), 3.63 (s, 3H), 3.37, 3.03 (2 x d(ab), J = 4.0 Hz, 2H), 2.35-2.05 (m, 3H),.82-.52 (m, 3H); 3 C NMR (75 MHz, CDCl 3 ): δ 25.0, 7.7, 58.8, 28.0, 3.6, 03.3, 60., 55.3, 52.4, 37.7, 3.7, 27.2, 9.4; HRMS (ESI): calculated for C 6 H 20 5 [M+H] + 293.384, found 293.379. Reaction using -tert-butyl 6-methyl 2-methylenehexanedioate (0) (4 mg, 0.5 mmol) as starting, -alkene: [0, 3] tert-butyl -benzyl-2-oxocyclopentanecarboxylate (26a): cyclic product (26a) was obtained as a colourless oil (9 mg, 87% yield). H NMR (300 MHz, CDCl 3 ): δ 7.20-7. (m, 3H), 7.08-7.04 (m, 2H), 3.04 (s, 2H), 2.33-2.20 (m, 2H),.94-.72 (m, 3H),.57-.4 (m, H),.35 (s, 9H); 3 C NMR (75 MHz, CDCl 3 ): δ 25.5, 70.3, 36.9, 29.0, 28.3, 26.6, 82.0, 6.9, 38.7, 38.3, 3.9, 27.8,

9.5; MS (EI): m/z 274 ([M + ], ), 28 (5), 200 (20), 73 (5), 72 (30), 7 (5), 55 (20), 45 (25), 30 (40), 29 (20), 28 (0), 7 (30), 6 (20), 5 (55), 9 (00), 78 (0), 65 (5), 57 (95); HRMS (EI): calculated for C 7 H 22 3 [M+NH 4 ] + 292.907, found 292.908. tert-butyl -(4-fluorobenzyl)-2-oxocyclopentanecarboxylate (26b): F cyclic product (26b) was obtained as a colourless oil (20 mg, 82% yield). H NMR (300 MHz, CDCl 3 ): δ 7.08-7.00 (m, 2H), 6.86 (tm, 2H, J = 9.0 Hz), 3.00 (s, 2H), 2.37-2.2 (m, 2H),.96-.75 (m, 3H),.60-.48 (m, H),.35 (s, 9H); 3 C NMR (75 MHz, CDCl 3 ): δ 25.3, 70.2, 6.7 (d, J = 245.4 Hz), 32.6, 3.8 (d, J = 6.8 Hz), 5.0 (d, J = 2. Hz), 8., 6.9, 38.2, 37.7, 3.9, 27.8, 9.4; MS (EI): m/z 292 ([M + ], 3), 236 (25), 29 (0), 9 (0), 90 (25), 73 (0), 48 (20), 47 (0), 35 (20), 34 (5), 33 (30), 5 (0), 09 (00), 96 (0), 83 (0), 57 (90); HRMS (EI): calculated for C 7 H 2 F 3 [M+NH 4 ] + 30.83, found 30.86. tert-butyl -(naphthalen--ylmethyl)-2-oxocyclopentanecarboxylate (26c): [0] cyclic product (26c) was obtained as a colourless oil (33 mg, 82% yield). H NMR (300 MHz, CDCl 3 ): δ 7.99 (d, J = 8.4 Hz, H), 7.74 (d, J = 8.4 Hz, H), 7.63 (d, J = 8.4 Hz, H), 7.40 (quintet x m, J = 8.4 Hz, 2H), 7.30-7.8 (m, 2H), 3.72, 3.49 (2 x d(ab), J = 4.0 Hz, 2H), 2.34-2.9 (m, 2H),.83-.52 (m, 3H),.42-.30 (m, H),

.36 (s, 9H); 3 C NMR (75 MHz, CDCl 3 ): δ 25.6, 70.8, 33.7, 33.5, 33., 28.7, 28., 27.4, 25.9, 25.5, 25.4, 24.2, 82., 62.4, 38.0, 33.7, 32.3, 27.8, 9.5; MS (EI): m/z 324 ([M + ], 5), 268 (0), 25 (0), 250 (25), 205 (25), 78 (0), 66 (0), 65 (55), 53 (0), 52 (25), 42 (25), 4 (80), 28 (60), 5 (30), 96 (0), 57 (00); HRMS (EI): calculated for C 2 H 24 3 [M+NH 4 ] + 342.2064, found 342.2063. tert-butyl -(3-methylbenzyl)-2-oxocyclopentanecarboxylate (26d): cyclic product (26d) was obtained as a colourless oil (28 mg, 89% yield). H NMR (300 MHz, CDCl 3 ): δ 7.09-7.03 (m, H), 6.95-6.9 (m, H), 6.88-6.82 (m, 2H), 3.0 (s, 2H), 2.43-2.20 (m, 2H), 2.24 (s, 3H),.98-.72 (m, 3H),.60-.45 (m, H),.35 (s, 9H); 3 C NMR (75 MHz, CDCl 3 ): δ 25.3, 70.3, 37.7, 36.8, 3.0, 28., 27.3, 27.0, 8.9, 6.9, 38.6, 38.3, 3.9, 27.8, 2.3, 9.5; MS (EI): m/z 288 ([M + ], ), 25 (25), 24 (55), 87 (20), 86 (20), 7 (35), 68 (20), 59 (40), 44 (5), 43 (0), 3 (25), 30 (5), 29 (30), 28 (20), 6 (5), 5 (40), 05 (00), 92 (20), 9 (30), 84 (20), 77 (20), 57 (95); HRMS (EI): calculated for C 8 H 24 3 [M+NH 4 ] + 306.2064, found 306.2064. tert-butyl -(3,5-dimethylbenzyl)-2-oxocyclopentanecarboxylate (26e): cyclic product (26e) was obtained as a colourless oil (9 mg, 79% yield). H NMR (300 MHz, CDCl 3 ): δ 6.76 (br s, H), 6.67 (br s, 2H), 3.0, 2.9 (2 x d(ab), J = 4.0 Hz, 2H), 2.32-2.6 (m, 2H), 2.20 (s, 6H),.98-.7 (m, 3H),.59-.47 (m, H),.35

(s, 9H); 3 C NMR (75 MHz, CDCl 3 ): δ 25.3, 70.3, 37.6, 36.8, 28.3, 28.0, 8.9, 62.0, 38.6, 38.3, 3.9, 27.9, 2., 9.5; MS (EI): m/z 302 ([M + ], ), 229 (5), 228 (40), 85 (20), 73 (20), 57 (0), 30 (0), 29 (20), 28 (20), 27 (0), 20 (5), 9 (00), 5 (20), 06 (20), 05 (5), 84 (0), 77 (0), 57 (60); HRMS (EI): calculated for C 9 H 26 3 [M+NH 4 ] + 320.2220, found 320.227. Reaction using dimethyl 2-methyleneheptanedioate (2) (00 mg, 0.5 mmol) as starting, -alkene: Methyl -benzyl-2-oxocyclohexanecarboxylate (24a): [4] cyclic product (24a) was obtained as a colourless oil (07 mg, 87% yield). H NMR (300 MHz, CDCl 3 ): δ 7.20-7.0 (m, 3H), 7.04-6.98 (m, 2H), 3.56 (s, 3H), 3.24, 2.79 (2 x d(ab), J = 4.0 Hz, 2H), 2.48-2.26 (m, 3H),.99-.88 (m, H),.70-.50 (m, 3H),.42-.33 (m, H); 3 C NMR (75 MHz, CDCl 3 ): δ 207., 7.3, 36.4, 30.2, 28.0, 26.6, 62.2, 52.2, 4.3, 40.4, 35.7, 27.5, 22.4; MS (EI): m/z 246 ([M + ], 3), 228 (20), 86 (20), 85 (25), 69 (0), 58 (0), 29 (0), 7 (20), 5 (35), 9 (00), 77 (0), 69 (0), 65 (25), 59 (0); HRMS (EI): calculated for C 5 H 8 3 [M+H] + 247.329, found 247.329. Methyl -(4-fluorobenzyl)-2-oxocyclohexanecarboxylate (24b): cyclic product (24b) was obtained as a colourless oil (98 mg, 74% yield). H NMR F

(300 MHz, CDCl 3 ): δ 7.09-7.02 (m, 2H), 6.90 (tm, J = 9.0 Hz, 2H), 3.6 (s, 3H), 3.20, 2.80 (2 x d(ab), J = 4.0 Hz, 2H), 2.52-2.26 (m, 3H), 2.05-.95 (m, H),.77-.36 (m, 4H); 3 C NMR (75 MHz, CDCl 3 ): δ 207., 7.4, 6.8 (d, J = 244.6 Hz), 32.3 (d, J = 3.0 Hz), 3.7 (d, J = 6.8 Hz), 4.8 (d, J = 2. Hz), 62.3, 52.2, 4.3, 39.6, 36.0, 22.5; MS (EI): m/z 264 ([M + ], 5) 246 (0), 204 (0), 76 (0), 35 (0), 33 (20), 09 (00), 83 (5), 67 (0), 59 (25); HRMS (EI): calculated for C 5 H 7 F 3 [M+NH 4 ] + 282.505, found 282.499. Methyl -(naphthalen--ylmethyl)-2-oxocyclohexanecarboxylate (24c): cyclic product (24c) was obtained as a colourless oil (29 mg, 93% yield). H NMR (300 MHz, CDCl 3 ): δ 7.9-7.85 (m, H), 7.77-7.7 (m, H), 7.65 (d, J = 8.4 Hz, H), 7.4-7.28 (m, 3H), 7.2-7.7 (m, H), 3.8, 3.3 (2 x d(ab), J = 4.0 Hz, 2H), 3.39 (s, 3H), 2.50-2.29 (m, 3H),.99-.88 (m, H),.66-.40 (m, 4H); 3 C NMR (75 MHz, CDCl 3 ): δ 207., 7.4, 33.7, 32.9, 32.8, 28.7, 28.5, 27.5, 25.6, 25.3, 25.0, 23.9, 62.0, 52., 4.2, 36.2, 35.5, 27.5, 22.6; MS (EI): m/z 296 ([M + ], ), 278 (0), 29 (0), 65 (25), 52 (5), 42 (5), 4 (00), 28 (5), 5 (40), 55 (25); HRMS (EI): calculated for C 2 H 24 3 [M+NH 4 ] + 34.75, found 34.752. Reaction using -tert-butyl 7-methyl 2-methyleneheptanedioate (3) (2 mg, 0.5 mmol) as starting, -alkene: tert-butyl -benzyl-2-oxocyclohexanecarboxylate (27a): [3,5]

cyclic product (27a) was obtained as a colourless oil (28 mg, 89% yield). H NMR (300 MHz, CDCl 3 ): δ 7.20-7.05 (m, 5H), 3.8, 2.80 (2 x d(ab), J = 4.0 Hz, 2H), 2.45-2.36 (m, 2H), 2.30-2.23 (m, H),.99-.88 (m, H),.70-.44 (m, 3H),.40-.20 (m, H),.20 (s, 9H); 3 C NMR (75 MHz, CDCl 3 ): δ 207.5, 70., 36.8, 30.6, 27.8, 26.5, 8.9, 62.4, 4.2, 40.3, 36.3, 27.8, 27.5, 22.6; MS (EI): m/z 288 ([M + ], ), 24 (0), 86 (0), 69 (0), 5 (5), 9 (40), 77 (0), 65 (0), 57 (00); HRMS (EI): calculated for C 2 H 24 3 [M+NH 4 ] + 306.2064, found 306.2063. tert-butyl -(4-fluorobenzyl)-2-oxocyclohexanecarboxylate (27b): cyclic product (27b) was obtained as a colourless oil (82 mg, 62% yield). H NMR (300 MHz, CDCl 3 ): δ 7.0-7.04 (m, 2H), 6.85 (tm, J = 9.0 Hz, 2H), 3.4, 2.76 (2 x d(ab), J = 4.0 Hz, 2H), 2.48-2.39 (m, 2H), 2.35-2.23 (m, H), 2.00-.89 (m, H),.70-.23 (m, 4H),.26 (s, 9H); 3 C NMR (75 MHz, CDCl 3 ): δ 207.7, 70., 6.7 (d, J = 244.6 Hz), 32.5 (d, J = 3.0 Hz), 32.2 (d, J = 6.8 Hz), 4.6 (d, J = 2. Hz), 82.2, 62.5, 4.3, 39.5, 36.5, 27.8, 22.6; MS (EI): m/z 306 ([M + ], ), 250 (20), 233 (0), 232 (20), 205 (0), 204 (40), 87 (20), 76 (0), 47 (0), 35 (20), 33 (25), 09 (90), 83 (20), 67 (0), 57 (00); HRMS (EI): calculated for C 8 H 23 F 3 [M+H] + 307.704, found 307.704. F tert-butyl -(naphthalen--ylmethyl)-2-oxocyclohexanecarboxylate (27c):

cyclic product (27c) was obtained as a colourless oil (07 mg, 63% yield). H NMR (300 MHz, CDCl 3 ): δ 8.00 (d, J = 8.4 Hz, H), 7.75 (d, J = 8.4 Hz, H), 7.65 (d, J = 8.4 Hz, H), 7.4-7.28 (m, 4H), 3.70, 3.40 (2 x d(ab), J = 4.0 Hz, 2H), 2.49-2.39 (m, 2H), 2.34-2.25 (m, H),.98-.88 (m, H),.62-.30 (m, 4H),.5 (s, 9H); 3 C NMR (75 MHz, CDCl 3 ): δ 207.5, 70.3, 33.7, 33.5, 33., 28.8, 28.6, 27.2, 25.6, 25.2, 25., 24.6, 82.0, 62.9, 4.3, 36.7, 34.6, 27.6, 27.5, 22.7; MS (EI): m/z 338 ([M + ], 3), 264 (5), 29 (5), 65 (25), 52 (0), 42 (0), 4 (00), 28 (20), 5 (5), 57 (75); HRMS (EI): calculated for C 22 H 26 3 [M+Na] + 36.774, found 36.772. 6-Isopropyl -methyl 2-benzylhexanedioate (28): The reaction was performed following the general procedure on 0.5 mmol of, - alkene. The,4-addition product (28) was obtained as a mixture with the cyclopentanone (23a) (30/70) and the products could not be separated by column chromatography. Interpretation of the NMR spectra of the mixture afforded: H NMR (300 MHz, CDCl 3 ): δ 7.8-6.94 (m, 5H), 4.8 (heptet, J = 6.0 Hz, H), 3.43 (s, 3H), 2.85-2.75 (m, H), 2.6-2.43 (m, 2H), 2.6 (t, J = 7. Hz, 2H),.95-.73 (m, 4H),.08 (d, J = 6.0 Hz, 6H); 3 C NMR (75 MHz, CDCl 3 ): δ 75.7, 72.8, 39., 28.8, 26.9, 26.4, 67.5, 5.5, 47.3, 38.5, 34.4, 3.3, 22.8, 2.8. 6-tert-Butyl -methyl 2-benzylhexanedioate (29): The reaction was performed following the general procedure on 0.5 mmol of, - alkene. After purification, the,4-addition product (29) was obtained as a colourless

oil (00 mg, 88% yield). H NMR (300 MHz, CDCl 3 ): δ 7.22-7.05 (m, 5H), 3.5 (s, 3H), 2.90-2.80 (m, H), 2.70-2.50 (m, 2H), 2. (t, J = 7. Hz, 2H),.60-.35 (m, 4H),.32 (s, 9H); 3 C NMR (75 MHz, CDCl 3 ): δ 75.8, 72.6, 39., 28.8, 28.4, 26.4, 80.2, 5.5, 47.4, 38.5, 35.3, 3.3, 28.0, 22.9; MS (EI): m/z 306 ([M + ], <), 250 (20), 232 (0), 20 (30), 90 (50), 73 (70), 55 (0), 3 (20), 30 (40), 7 (20), 9 (00), 77 (0), 65 (5), 57 (85), 55 (5); HRMS (EI): calculated for C 8 H 26 4 [M+NH 4 ] + 324.269, found 324.269. Methyl 2-benzyl-6-oxo-6-(pyrrolidin--yl)hexanoate (30): N The reaction was performed following the general procedure on 0.5 mmol of, - alkene. After purification, the,4-addition product (30) was obtained as a colourless oil (37 mg, 90% yield). H NMR (300 MHz, CDCl 3 ): δ 7.3-6.92 (m, 5H), 3.40 (s, 3H), 3.25 (t, J = 6.9 Hz, 2H), 3.5 (t, J = 6.9 Hz, 2H), 2.80-2.70 (m, H), 2.62-2.45 (m, 2H), 2.09-2.0 (m, 2H),.80-.59 (m, 4H),.57-.35 (m, 4H); 3 C NMR (75 MHz, CDCl 3 ): δ 75.8, 70.9, 39., 28.7, 28.2, 26.2, 5.3, 47.4, 46.4, 45.5, 38.4, 34.3, 3.7, 26.0, 24.3, 22.6; MS (EI): m/z 303 ([M + ], 5), 66 (0), 40 (20), 26 (50), 3 (00), 98 (45), 9 (70), 85 (20), 70 (70), 55 (65); HRMS (EI): calculated for C 8 H 25 N 3 [M+H] + 304.907, found 304.906. References: [] K. J. Wadsworth, F. K. Wood, C. J. Chapman, C. G. Frost, Synlett 2004, 2022-2024. [2] C. S. Yi, N. H. Liu, J. rganomet. Chem. 998, 553, 57-6. [3] E. Charonnet, M.-H. Filippini, R. J., Synthesis 200, 788-804. [4] N. El Ghandour, B. Souiller, Bull. Soc. Chim. Fr. 97, 2290-229. [5] M. E. Fox, M. Jackson, I. C. Lennon, R. McCague, J. rg. Chem. 2005, 70, 227-236. [6] B. Kalita, K. M. Nicholas, Tetrahedron 2004, 60, 077-0778.

[7] V. Chaleix, V. Sol, Y. M. Huang, M. Guilloton, R. Granet, J. C. Blais, P. Krausz, Eur. J. rg. Chem. 2003, 486-493. [8] S. Isomura, P. Wirsching, K. D. Janda, J. rg. Chem. 200, 66, 45-42. [9] N. Minowa, T. Mukaiyama, Chem. Lett. 987, 79-722. [0] K. Manabe, Tetrahedron 998, 54, 4465-4476. [] A. Kato, Y. Ikeda, N. Sugita, T. Nitta, H. Enari, A. Kashima, M. Konno, K. Niimura, Chem. & Pharm. Bull. 995, 43, 252-258. [2] K. hkata, Bull. Chem. Soc. Jpn. 976, 49, 235-244 [3] D. Henderson, K. A. Richardson, R. J. K. Taylor, J. Saunders, Synthesis 983, 996-997. [4] a) K. Kato, H. Suemune, K. Sakai, Tetrahedron 994, 50, 335-3326; b) D. A. Jeyaraj, K. K. Kapoor, V. K. Yadav, H. M. Gauniyal, M. Parvez, J. rg. Chem. 998, 63, 287-294. [5] T. oi, T. Miki, M. Taniguchi, M. Shiraishi, M. Takeuchi, K. Maruoka, Angew. Chem. Int. Ed. 2003, 42, 3796-3798. 2