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1 doi: /nature12761 Materials and Methods General Unless otherwise noted, all reactions were carried out under an atmosphere of argon, and all reagents were purchased from commercial suppliers and used without further purification. All reactions were carried out in flame-dried glassware under positive pressure of argon in dry solvents using standard Schlenk techniques. Progress of the reactions was monitored by analytical TLC using glass plates precoated with silica gel with F254 indicator (Merck). Visualization of spots was done using UV light (254 nm), p-anisaldehyde or KMnO 4 solutions followed by heating. All organometallic compounds, dry solvents and reagents were transferred using plastic single-use graduated syringes and oven-dried stainless steel needles. n-buli, is commercially obtained from Aldrich and titrated under argon atmosphere by 1M solution of 2-isobutanol in toluene, using 1,10-phenantroline as indicator. Aldehydes or ketones were purchased from commercial suppliers and distilled prior to use. Purification of crude mixtures was accomplished by flash column chromatography on silica gel 60 Å (GraceResolv). 1 H and 13 C NMR spectra were measured on Brucker Avance DPX 200 (200 MHz), AV 300 (300 MHz) or AV 400 (400 MHz) spectrometer. Chemical shifts values (δ) are reported in ppm (calibration of spectra to the residual peak of CDCl 3 : δ = 7.26 ppm (s) for 1 H NMR; δ = ± 0.06 ppm for 13 C NMR). All the proton spectra reported as following: δ value (multiplicity, J coupling constant in Hz, number of nuclei). Multiplicity contractions used: (s) singlet, (d) doublet, (dd) doublet of doublet, (dt) doublet of triplet, (dq) doublet of quartet, (ddt) double doublet of triplets, (t) triplet, (q) quartet, (m) multiplet, (bs) broad singlet, (b) broad signal. All starting materials, cyclopropanes 1a-1h, alkylidenecyclopropanes 2a-2j and cyclopropanes 5a-5g, were prepared by reactions reported in the literature (31, 32, 33, 34, 35, 36) and experimental data were identical to those reported. 1

2 General Procedure (Procedure A) for the tandem zirconocene-mediated allylic C,H activation carboncarbon bond cleavage of ω-alkenyl cyclopropopanes 1a-h followed by hydrolysis. R 1 R 2 n Cp 2 ZrC 4 H 8, Et 2 O -78 C to rt, 12 h CH 3 then H 3 O + n-1 R 1 R 2 Into a flame-dried, 50-mL three-neck flask, containing a solution of bis(cyclopentadienyl)zirconium dichloride (292 mg, 1 mmol) in dry Et 2 O (10 ml) and equipped with a magnetic stirrer, a low temperature thermometer, a rubber septum and an inert gas inlet, was added a solution of n-butyllithium (1.6 M in hexane, 1.25 ml, 2 mmol) at -78 C under inert atmosphere. After stirring for 1 hour at -78 C, substrates 1a-e (0.5 mmol), diluted in 2 ml of dry Et 2 O were added to the solution at -78 C. The resulting mixture was allowed to slowly warm-up to room temperature over night (12 h). The bismetallated allyl-alkyl zirconocene species were then hydrolyzed (or deuterolyzed) with an aqueous solution of 1M HCl (or D 2 O). The layers were separated and the aqueous phase was extracted with Et 2 O (5 times). The combined organic fractions were washed with a saturated solution of NaHCO 3 and dried over Na 2 SO 4(s) and concentrated under reduced pressure to give crude oils. The products 4a-e were obtained pure by silica-gel chromatography using n-hexane as eluent. (E)-2,2-diphenylhex-3-ene, 4a 4a The corresponding compound was prepared following general procedure A using 1a. Purification by flash chromatography (hexane) afforded the product as a colorless oil (84 mg, 71% yield). 1 H NMR (CDCl 3, 400 MHz) δ 1.03 (t, J = 7.6 Hz, 3H), 1.79 (s, 3H), (m, 2H), 5.35 (dt, J = 15.6 Hz, 6.4 Hz, 1H), 5.99 (d, J = 15.6 Hz, 1H), (m, 10H). 13 C NMR (CDCl 3, 100 MHz) δ 14.1, 25.9, 28.0, 49.3, 125.9, 128.0, 128.1, 130.7, 137.7, HRMS (EI) calcd. for C 18 H 20 [M] + : , found: (E)-2,2-diphenyl-(1,5-2 H 2 )hex-3-ene, 4a(D) 4a(D) The corresponding compound was prepared following general procedure A using 1a. Purification by flash chromatography (hexane) afforded the product as a colorless oil (85 mg, 71% yield). 1 H NMR (CDCl 3, 400 MHz) δ 0.98 (d, J = 7.2 Hz, 3H), 1.74 (b, 2H), (m, 1H), 5.31 (dd, J = 15.6 Hz, 6.0 Hz, 1H), 5.95 (dd, J = 15.6 Hz, 2

3 1 Hz, 1H), (m, 10H). 13 C NMR (CDCl 3, 100 MHz) δ 14.0, 25.6 (t, J = 19.1 Hz), 27.7 (t, J = 19.1 Hz), 49.3, 125.9, 128.0, 128.1, 130.6, 137.8, HRMS (EI) calcd. for C 18 H 18 D 2 + [M] + : , found: (E)-2,2-diphenylhept-3-ene, 4b 4b The corresponding compound was prepared following general procedure A using 1b. Purification by flash chromatography (hexane) afforded the product as a colorless oil (73 mg, 58% yield). 1 H NMR (CDCl 3, 400 MHz) δ 0.83 (t, J = 7.2 Hz, 3H), (m, 2H), 1.68 (s, 3H), (m, 2H), 5.19 (dt, J = 15.6 Hz, 6.8 Hz, 1H), 5.85 (d, J = 15.6 Hz, 1H), (m, 10H). 13 C NMR (CDCl 3, 100 MHz) δ 14.1, 22.8, 28.1, 31.9, 32.6, 49.5, 125.9, 128.0, 128.1, 129.2, 138.6, (E)-2,2-diphenyloct-3-ene, 4c 4c The corresponding compound was prepared following general procedure A using 1c. Purification by flash chromatography (hexane) afforded the product as a colorless oil (81 mg, 61% yield). 1 H NMR (CDCl 3, 400 MHz) δ 0.91 (t, J = 7.2 Hz, 3H), (m, 4H), 1.78 (s, 3H), (m, 2H), 5.30 (dt, J = 15.6 Hz, 6.8 Hz, 1H), 5.98 (d, J = 15.6 Hz, 1H), (m, 10H). 13 C NMR (CDCl 3, 100 MHz) δ 14.1, 22.5, 26.1, 31.9, 32.6, 49.5, 125.9, 128.0, 128.1, 129.2, 138.6, HRMS (API) calcd. for C 20 H 24 [M] + : , found: (E)-2,2-diphenylundec-3-ene, 4d 4d The corresponding compound was prepared following general procedure A using 1d. Purification by flash chromatography (hexane) afforded the product as a colorless oil (84 mg, 55% yield). 1 H NMR (CDCl 3, 400 MHz) δ 0.90 (t, J = 6.8 Hz, 3H), (m, 10H), 1.78 (s, 3H), 2.09 (q, J = 6.7 Hz, 2H), 5.30 (dt, J = 15.6 Hz, 6.8 Hz, 1H), 5.98 (d, J = 15.6 Hz, 1H), (m, 10H). 13 C NMR (CDCl 3, 100 MHz) δ 14.3, 22.8, 28.1, 29.3, 29.4, 29.7, 32.0, 32.9, 49.5, 125.9, 128.0, 128.1, 129.3, 138.7, (E)-2-methyl-2-phenylhex-3-ene, 4e 4e 3

4 The corresponding compound was prepared following general procedure A using 1e. Purification by flash chromatography (hexane) afforded the product as a colorless oil (74 mg, 85% yield). 1 H NMR (CDCl 3, 400 MHz) δ 0.99 (t, J = 7.2 Hz, 3H), 1.37 (s, 6H), (m, 2H), 5.47 (dt, J = 15.6 Hz, 6.4 Hz, 1H), 5.61 (d, J = 15.6 Hz, 1H), (m, 5H). 13 C NMR (CDCl 3, 100 MHz) δ 14.2, 25.8, 29.1, 40.3, 125.7, 126.3, 128.1, 128.3, 139.1, HRMS (API) calcd. for C 13 H + 19 [M+H] + : , found: General Procedure (Procedure B) for the tandem zirconocene-mediated allylic C,H activation carboncarbon bond cleavage of ω-alkenyl cyclopropopanes 1a,d followed by addition of two different electrophiles. R 1 R 2 n 1) Cp 2 ZrC 4 H 8, Et 2 O -78 C to rt, 12 h 2) E 1 -X 3) E 2 -X then H 3 O + E 2 CH 3 R 1 R 2 E 1 n-1 Into a flame-dried, 50-mL three-neck flask, containing a solution of bis(cyclopentadienyl)zirconium dichloride (292 mg, 1 mmol) in dry Et 2 O (10 ml) and equipped with a magnetic stirrer, a low temperature thermometer, a rubber septum and an inert gas inlet, was added a solution of n-butyllithium (1.6 M in hexane, 1.25 ml, 2 mmol) at -78 C under inert atmosphere. After stirring for 1 hour at -78 C, substrates 1a,f,d (0.5 mmol), diluted in 2 ml of dry Et 2 O were added to the solution at -78 C. The resulting mixture was allowed to slowly warm-up to room temperature over night (12 h). The bismetallated allyl-alkyl zirconocene species is ready for further use. The first electrophile (1.25 mmol) is added to the reaction mixture at -30 C and stirred for 1 hour. The second electrophile (1.25 mmol) is then added and stirred for an additional 1 hour at -30 C and slowly warmed at room temperature. Finally, the reaction mixture is hydrolyzed with an aqueous solution of 1M HCl. The layers were separated and the aqueous phase was extracted with Et 2 O (5 times). The combined organic fractions were washed with an aqueous solution of NaHCO 3 and dried over Na 2 SO 4(s) and concentrated under reduced pressure to give crude oil. The product 4 was obtained pure by silica-gel chromatography using gradient mixtures of ethyl acetate and n-hexane as eluents. (E)-2,3-dimethyl-6,6-diphenylhept-4-en-2-ol, 4f 4f The corresponding compound was prepared following general procedure B using 1a with E 1 -X = CH 3 COCH 3 and E 2 -X = H 3 O +. Purification by flash chromatography (hexane) afforded the product as a colorless oil (82 mg, 56% yield). 1 H NMR (CDCl 3, 400 MHz) δ 1.04 (d, J = 8.0 Hz, 3H), 1.12 (s, 3H), 1.15 (s, 3H), 1.53 (bs, 1H, OH), 1.79 (s, 4

5 3H), 2.28 (dq, J = 9.0 Hz, 6.8 Hz, 1H), 5.26 (dd, J = 15.3 Hz, 9.0 Hz, 1H), 6.09 (dd, J = 15.3 Hz, 0.8 Hz, 1H), (m, 10H). 13 C NMR (CDCl 3, 100 MHz) δ 15.7, 27.0, 27.1, 28.1, 48.5, 49.6, 72.7, 126.0, 126.1, 127.8, 127.9, 128.1, 128.2, 130.7, 140.8, 148.6, HRMS (ESI) calcd. for C 21 H 26 ONa + [M+Na] + : , found: (E)-6-butyl-2,3,6-trimethyldec-4-en-2-ol, 4g 4g The corresponding compound was prepared following general procedure B using 1f with E 1 -X = CH 3 COCH 3 and E 2 -X = H 3 O +. Purification by flash chromatography afforded the product as a colorless oil (95 mg, 75% yield). 1 H NMR (CDCl 3, 400 MHz) δ 0.86 (t, J = 7.6 Hz, 6H), 0.91 (s, 3H), 1.00 (d, J = 7.2 Hz, 3H), 1.12 (s, 3H), 1.17 (s, 3H), (m, 12H), 1.64 (bs, 1H, OH), 2.15 (dq, J = 8.4 Hz, 6.4 Hz, 1H), 5.17 (dd, J = 15.6 Hz, 8.4 Hz, 1H), 5.37 (d, J = 15.6 Hz, 1H). 13 C NMR (CDCl 3, 100 MHz) δ 14.3, 16.2, 23.5, 23.6, 26.4, 26.5, 26.7, 27.0, 38.8, 41.2, 41.3, 48.8, 72.3, 128.4, HRMS (ESI) calcd. for C 17 H 34 ONa + [M+Na] + : , found: (E)-6-butyl-6-(iodomethyl)-2,3-dimethyldec-4-en-2-ol, 4h 4h The corresponding compound was prepared following general procedure B using 1f with E 1 -X = CH 3 COCH 3 and E 2 -X = I 2. Purification by flash chromatography afforded the product as a colorless oil (101 mg, 53% yield). 1 H NMR (CDCl 3, 400 MHz) δ 0.89 (t, J = 7.2 Hz, 3H), 0.90 (t, J = 7.6 Hz, 3H), 1.02 (d, J = 7.2 Hz, 3H), (m, 4H), 1.16 (s, 3H), 1.19 (s, 3H), (m, 8H), 1.74 (bs, 1H, OH), (m, 1H), 3.17 (d, J = 9.8 Hz, 1H), 3.21 (d, J = 9.8 Hz, 1H), (m, 2H). 13 C NMR (CDCl 3, 100 MHz) δ 14.2, 14.3, 16.1, 20.8, 23.4, 26.0, 26.4, 26.5, 27.3, 36.1, 36.8, 41.5, 48.9, 72.5, 131.8, HRMS (ESI) calcd. for C 17 H 33 IO + [M] + : , found: (E)-3-(3,3-diphenylbut-1-en-1-yl)-2-methylnonan-2-ol, 4i 4i The corresponding compound was prepared following general procedure B using 1d with E 1 -X = CH 3 COCH 3 and E 2 -X = H 3 O +. Purification by flash chromatography (hexane) afforded the product as a colorless oil (100 mg, 55% yield). 1 H NMR (CDCl 3, 400 MHz) δ 0.82 (t, J = 6.4 Hz, 3H), 1.07 (s, 3H), 1.12 (s, 3H), (m, 10H),

6 (br s, 1H), 1.79 (s, 3H), (m, 1H), 5.02 (dd, J = 15.6 Hz, 10.0 Hz, 1H), 6.08 (d, J = 15.6 Hz, 1H), (m, 10H). 13 C NMR (CDCl 3, 100 MHz) δ 14.3, 22.7, 27.1, 27.4, 28.3, 29.2, 29.4, 32.0, 50.0, 55.2, 72.6, 126.0, 126.1, 127.8, 127.9, 128.1, 128.2, 129.4, 143.0, 148.5, HRMS (ESI) calcd. for C 26 H 36 ONa + [M+Na] + : , found: General Procedure (Procedure C) for the tandem zirconocene-mediated allylic C,H activation carboncarbon bond cleavage of alkylidenecyclopropopanes 2 followed by hydrolysis. R 1 R 2 R 3 Cp 2 ZrC 4 H 8, Et 2 O -78 C to rt, 12 h then H 3 O + R 3 R 1 R 2 To a solution of zirconocene dichloride (496.5 mg, 1.70 mmol) in Et 2 O (45 ml) cooled to -78 C was added dropwise n-buli (1.40 M in hexane, 2.4 ml, 3.4 mmol). The resulting solution was stirred for 1 h at -78 C. A solution of alkylidenecyclopropane (1.00 mmol) in Et 2 O (5 ml) was added, and the reaction mixture was slowly warmed to 10 C. After stirring for 13 h, the mixture was quenched with an aqueous solution of HCl (1 M) while cooling to 0 C and extracted with Et 2 O. The organic extracts were washed with water, NaHCO 3 and brine, dried (MgSO 4 ), filtered, and concentrated in vacuo to give a crude oil. Purification was performed by column chromatography on silica gel with hexane as eluent. (R,E)-4-ethyl-4-methyloct-2-ene, 4k (37) 4k The corresponding compound was prepared following general procedure C using 2b. Purification by flash chromatography (hexane) afforded the product 4k as a colorless oil (84% yield). Enantiomeric ratio of 4k is 98:2 [α] 25 D = (c = 10 mg/ml, CDCl 3 ) (37) and is identical to the enantiomeric ratio of the starting alkylidenecyclopropane 2b (33). 1 H NMR (CDCl 3, 300 MHz) δ 0.77 (t, J = 7.4 Hz, 3H), 0.89 (t, J = 6.6 Hz, 3H), 0.90 (s, 3H), (m, 10H), (m, 3H), (m, 2H). 13 C NMR (CDCl 3, 75 MHz) δ 8.3, 14.1, 18.1, 22.7, 23.5, 26.2, 33.4, 38.4, 40.6, 121.2, HRMS (ESI pos) calcd. for C 11 H + 23 [M+H] + : , found: (E)-5-methyl-5-phenylhept-3-ene, 4l 6

7 4l The corresponding compound was prepared following general procedure C using 2c. Purification by flash chromatography (hexane) afforded the product 4l as a colorless oil (92% yield). 1 H NMR (CDCl 3, 300 MHz) δ 0.82 (t, J = 7.5 Hz, 3H), 1.08 (t, J = 7.5 Hz, 3H), 1.39 (s, 3H), (m, 2H), 2.15 (dq, J 1 = 7.5 Hz, J 2 = 1.3 Hz, 2H), 5.53 (dt, J 1 = 6.3Hz, J 2 = 15.9Hz, 1H), 5.68 (dt, J 1 = 1.3Hz, J 2 = 15.9Hz, 1H), (m, 5H). 13 C NMR (CDCl 3, 75 MHz) δ 9.0, 14.1, 25.1, 25.9, 34.0, 43.5, , 126.7, 127.9, 129.2, 137.6, HRMS (ESI pos) Calcd. for C 14 H + 21 [M+H] + : , found: (E)-5,5-dimethyl-1-phenylnon-3-ene, 4m (38) 4m The corresponding compound was prepared following general procedure C using 2d. Purification by flash chromatography (hexane) afforded the product 4m as a colorless oil (92% yield). 1 H NMR (CDCl 3, 300 MHz) δ 0.83 (t, J = 7.1 Hz, 3H), 0.90 (s, 6H), (m, 6H), (m, 2H), 2.63 (dd, J 1 = 6.8 Hz, J 2 = 8.6 Hz, 2H), (m, 2H), (m, 5H). 13 C NMR (CDCl 3, 75 MHz) δ 14.5, 23.8, 27.1, 27.7, 27.7, 35.0, 35.9, 36.7, 43.3, 125.2, 125.9, 128.5, 128.8, 141.4, HRMS (ESI pos) calcd. for C 17 H + 27 [M+H] + : , found: (E)-5-methyl-1,5-diphenylhex-3-ene, 4n 4n The corresponding compound was prepared following general procedure C using 2e. Purification by flash chromatography (hexane) afforded the product 4n as a colorless oil (93% yield). 1 H NMR (CDCl 3, 300 MHz) δ 1.42 (s, 6H), (m, 2H), (m, 2H), 5.52 (dt, J 1 = 15.0 Hz, J 2 = 7.5 Hz, 1H), 5.67 (dt, J 1 = 15.0 Hz, J 2 = 1.5 Hz, 1H), (m, 10H). 13 C NMR (CDCl 3, 75 MHz) δ 23.4, 25.8, 36.1, 41.4, 43.4, 125.4, 125.7, 126.3, 126.6, 127.9, 128.2, 128.6, 139.8, 142.8, HRMS (ESI pos) calcd. for C 19 H + 23 [M+H] + : , found:

8 (E)-5-methyl-5-(( 2 H 1 )methyl)-1-phenyl(2-2 H 1 )hept-3-ene, 4o 4o To a solution of zirconocene dichloride (496.5 mg, 1.70 mmol) in Et 2 O (45 ml) cooled to -78 C was added dropwise n-buli (1.40 M in hexane, 2.4 ml, 3.4 mmol). The resulting solution was stirred for 1 h at -78 C. A solution of the alkylidenecyclopropane 2f (1.00 mmol) in Et 2 O (5 ml) was added, and the reaction mixture was slowly warmed to 10 o C. After stirring for 13 h, the mixture was quenched with an aqueous solution of DCl (1 M in D 2 O, 30 ml) while cooling to 0 C the mixture was stirred for 2 hours and then extracted with Et 2 O. The organic extracts were washed with water, NaHCO 3 and brine, dried (MgSO 4 ), filtered, and concentrated to give a crude oil. Purification was performed by column chromatography on silica gel with hexane as eluent. 4o was obtained as colorless oil in 90% yield. 1 H NMR (CDCl 3, 300 MHz) δ 0.75 (t, J = 7.5 Hz, 3H), (m, 2H), 0.93 (s, 3H), 1.27 (q, J = 6.0 Hz, 2H), (m, 1H), 2.67 (d, J = 7.8 Hz, 2H), (m, 2H), (m, 5H). 13 C NMR (CDCl 3, 75 MHz) δ 8.8, 26.4 (t, J = 19.1 Hz ), 26.7, 34.2 (t, J = 19.4 Hz ), 35.3, 35.6, 36.2, 125.0, 125.5, 128.1, 128.4, 140.7, HRMS (ESI pos) calcd. for C 15 H 20 D + 2 [M+H] + : , found: (E)-6,6-dimethyl(3,3,5-2 H 3 )dec-4-en-2-ol, 4j 4j To a solution of zirconocene dichloride (496.5 mg, 1.70 mmol) in Et 2 O (45 ml) cooled to -78 C was added dropwise n-buli (1.40 M in hexane, 2.4 ml, 3.4 mmol). The resulting solution was stirred for 1 h at -78 C. A solution of alkylidenecyclopropane 2a (1.00 mmol) in Et 2 O (5 ml) was added, and the reaction mixture was slowly warmed to 10 C. After stirring for 13 h, acetaldehyde (2.5 mmol) was added at 0 C and the reaction mixture was stirred for 20 min at the same temperature. An aqueous solution of HCl (1 M) was then added at 0 C and after classical treatment, 4j was purified by column chromatography on silica gel with hexane/etoac as eluent (20/1). 4j was obtained as colorless oil in 82% yield. 1 H NMR (CDCl 3, 300 MHz) δ 0.86 (t, J = 7.2 Hz, 3H), 0.95 (s, 6H), (m, 6H), 1.16 (d, J = 6.3 Hz, 3H), 1.82 (bs, 1H), 3.75 (q, J = 6.0 Hz, 1H), 5.25 (bs, 1H). 13 C NMR (CDCl 3, 75 MHz) δ 14.0, 22.3, 23.3, 26.8, 27.1, 27.2, 35.7, 41.8 (t, J = 18.8 Hz), 42.7, 67.0, 121.0, (d, J = 22.4 Hz). HRMS (ESI pos) calcd. for C 12 H 22 D 3 O + [M+H] + : , found: (E)-5,5-dimethyl-2-(phenylmethyl)hept-3-en-1-ol, 4p 8

9 4p To a solution of zirconocene dichloride (496.5 mg, 1.70 mmol) in Et 2 O (45 ml) cooled to -78 C was added dropwise n-buli (1.40 M in hexane, 2.4 ml, 3.4 mmol). The resulting solution was stirred for 1 h at -78 C. A solution of alkylidenecyclopropane 2f (1.00 mmol) in Et 2 O (5 ml) was added, and the reaction mixture was slowly warmed to 10 C. After stirring for 13 h, formaldehyde (2.5 mmol) was added at 0 C and the reaction mixture was stirred for 20 min at the same temperature. An aqueous solution of HCl (1 M) was then added at 0 C and after classical treatment, 4p was purified by column chromatography on silica gel with hexane/etoac as eluent (20/1). The title product was obtained as colorless oil in 90% yield. 1 H NMR (CDCl 3, 300 MHz) δ 0.68 (t, J = 7.5 Hz, 3H), 0.91 (s, 3H), 0.93 (s, 3H), 1.24 (q, J = 7.5 Hz, 2H), 1.5 (bs, 1H), (m, 1H), (m, 2H), (m, 2H), 5.11 (dd, J 1 = 8.4 Hz, J 2 = 15.6 Hz, 1H), 5.39 (dd, J 1 = 0.6 Hz, J 2 = 15.6 Hz, 1H), (m, 5H). 13 C NMR (CDCl 3, 75 MHz) δ 8.8, 26.5, 26.9, 35.2, 36.0, 38.0, 47.5, 65.2, 125.8, 126.0, 128.0, 129.1, 139.8, HRMS (ESI pos) calcd. for C 16 H 24 ONa + [M+Na] + : , found: (E)-6,6-dimethyldec-4-en-2-ol, 4q 4q To a solution of zirconocene dichloride (496.5 mg, 1.70 mmol) in Et 2 O (45 ml) cooled to -78 C was added dropwise n-buli (1.40 M in hexane, 2.4 ml, 3.4 mmol). The resulting solution was stirred for 1 h at -78 C. A solution of alkylidenecyclopropane 2g (1.00 mmol) in Et 2 O (5 ml) was added, and the reaction mixture was slowly warmed to 10 C. After stirring for 13 h, acetaldehyde (2.5 mmol) was added at 0 C and the reaction mixture was stirred for 20 min at the same temperature. An aqueous solution of HCl (1 M) was then added at 0 C and after classical treatment, 4q was purified by column chromatography on silica gel with hexane/etoac as eluent (20/1). The title product was obtained as colorless oil in 85% yield. 1 H NMR (CDCl 3, 300 MHz) δ 0.88 (t, J = 7.5 Hz, 3H), 0.97 (s, 6H), (m, 6H), 1.18 (d, J = 6.0 Hz, 3H), 1.70 (bs, 1H), (m, 2H), (m, 1H), 5.28 (ddd, J 1 = 6.0 Hz, J 2 = 7.5 Hz, J 3 = 15.8 Hz, 1H), 5.49 (dt, J 1 = 3.0 Hz, J 2 = 15.0 Hz, 1H). 13 C NMR (CDCl 3, 75 MHz) δ 14.0, 22.4, 23.3, 26.8, 27.2, 27.2, 35.8, 42.6, 42.7, 67.1, 121.2, HRMS (ESI pos) calcd. for C 12 H 25 O + [M+H] + : , found: (E)-3-benzyl-2,6-dimethyl-6-phenylhept-4-en-2-ol, 4r 4r To a solution of zirconocene dichloride (496.5 mg, 1.70 mmol) in Et 2 O (45 ml) cooled to -78 C was added dropwise n-buli (1.40 M in hexane, 2.4 ml, 3.4 mmol). The resulting solution was stirred for 1 h at -78 C. A 9

10 solution of alkylidenecyclopropane 2e (1.00 mmol) in Et 2 O (5 ml) was added, and the reaction mixture was slowly warmed to 10 C. After stirring for 13 h, acetone (2.5 mmol) was added at 0 C and the reaction mixture was stirred for 20 min at the same temperature. An aqueous solution of HCl (1 M) was then added at 0 C and after classical treatment, 4r was purified by column chromatography on silica gel with hexane/etoac as eluent (20/1). The title product was obtained as colorless oil in 92% yield. 1 H NMR (CDCl 3, 300 MHz) δ 1.21 (s, 3H), 1.28 (s, 3H), 1.30 (s, 3H), 1.32 (s, 3H), 1.60 (bs, 1H), (m, 1H), 2.47 (t, J = 12.3 Hz, 1H), 3.11 (dd, J 1 = 3.0 Hz, J 2 = 12.9 Hz, 1H), 5.24 (dd, J 1 = 9.3 Hz, J 2 = 15.6 Hz, 1H), 5.40 (d, J = 15.6 Hz, 1H), (m, 10H). 13 C NMR (CDCl 3, 75 MHz) δ 26.8, 27.6, 28.5, 28.8, 36.3, 40.5, 57.2, 72.3, 125.4, 125.5, 125.6, 125.9, 127.8, 128.1, 129.3, 141.0, 144.6, HRMS (ESI pos) calcd. for C 22 H 28 ONa + [M+Na] + : , found: (E)-6-benzyl-7-iodo-2,6-dimethylhept-4-en-2-ol, 4s 4s To a solution of zirconocene dichloride (496.5 mg, 1.70 mmol) in Et 2 O (45 ml) cooled to -78 C was added dropwise n-buli (1.40 M in hexane, 2.4 ml, 3.4 mmol). The resulting solution was stirred for 1 h at -78 C. A solution of alkylidenecyclopropane 2h (1.00 mmol) in Et 2 O (5 ml) was added, and the reaction mixture was slowly warmed to 10 C. After stirring for 13 h, acetone (2.5 mmol) was added at 10 C and the reaction mixture was stirring for 6 h at the same temperature. Then iodine (4 mmol) was added at 0 C and the mixture reaction was stirring for 3 h. An aqueous solution of HCl (1 M) was then added at 0 C and after classical treatment, 4s was purified by column chromatography on silica gel with hexane/etoac as eluent (20/1). The title product was obtained as yellow oil in 72% yield. 1 H NMR (CDCl 3, 300 MHz) δ 1.12 (s, 3H), 1.16 (s, 3H), 1.17 (s, 3H), 1.65 (bs, 1H), 2.17 (d, J = 6.6 Hz, 2H), 2.75 (s, 2H), 3.19 (s, 2H), (m, 2H), (m, 5H). 13 C NMR (CDCl 3, 75 MHz) δ 22.4, 24.2, 29.0, 29.1, 40.3, 45.7, 46.7, 70.4, 125.0, 126.4, 127.8, 130.3, 137.4, HRMS (ESI pos) calcd. for C 16 H 23 ONa + [M+Na] + : , found: (3S*,6R*,E)-2,3,6-trimethyl-6-phenylnon-4-en-2-ol, 4t 4t To a solution of zirconocene dichloride (496.5 mg, 1.70 mmol) in THF (45 ml) cooled to -78 C was added dropwise n-buli (1.40 M in hexane, 2.4 ml, 3.4 mmol). The resulting solution was stirred for 1 h at -78 C. A solution of alkylidenecyclopropane 2i (1.00 mmol) in THF (5 ml) was added, and the reaction mixture was slowly warmed to 10 C. After stirring for 13 h, then the reaction was heating to 60 o C for 6 hours. After cooling the reaction to 10 o C, acetone (5 mmol) was added at 10 C and the reaction mixture was stirred for 40 min at the same temperature. An aqueous solution of HCl (1 M) was then added at 10 C and the mixture was stirred for 1 hour and 10

11 after classical treatment, 4t was purified by column chromatography on silica gel with hexane/etoac as eluent (35/1). The title product was obtained as a yellow oil in 77% yield with a diastereomeric ratio of 98:02. 1 H NMR (CDCl 3, 300 MHz) of the major diastereomer ((3S*,6R*,E)-2,3,6-trimethyl-6-phenylnon-4-en-2-ol, 4t: δ 0.84 (t, J = 7.5 Hz, 3H), 1.02 (d, J = 6.9 Hz, 3H), 1.13 (s, 3H), 1.16 (s, 3H), 1.34 (s, 3H), 1.62 (br-s, 1H), (m, 4H), (m, 1H), 5.35 (dd, J 1 = 15.8 Hz, J 2 = 8.9 Hz, 1H), 5.70 (dd, J 1 = 15.8 Hz, J 2 = 1.0 Hz, 1H), (m, 5H). 13 C NMR (CDCl 3, 75 MHz) of the major diastereomer (3S*,6R*,E)-2,3,6-trimethyl-6-phenylnon-4-en-2-ol, 4t: δ 14.7, 15.7, 17.7, 25.4, 26.6, 26.9, 43.6, 44.0, 48.4, 72.5, 125.5, 126.4, 127.9, 128.6, 141.2, HRMS (ESI pos) calcd. for C 18 H 28 ONa + [M+Na] + : , found: (2S*,5R*,E)-2,5-dimethyl-5-phenyloct-3-en-1-ol, 4u 4u To a solution of zirconocene dichloride (496.5 mg, 1.70 mmol) in THF (45 ml) cooled to -78 C was added dropwise n-buli (1.40 M in hexane, 2.4 ml, 3.4 mmol). The resulting solution was stirred for 1 h at -78 C. A solution of alkylidenecyclopropane 2i (1.00 mmol) in THF (5 ml) was added, and the reaction mixture was slowly warmed to 10 C. After stirring for 13 h, then the reaction was heating to 60 o C for 6 hours. After cooling the reaction to 10 o C, paraformaldehyde (4 mmol) was added at 10 C and the reaction mixture was stirred for 2 hours at the same temperature. An aqueous solution of HCl (1 M) was then added at 10 C the mixture was stirred for 1 hour and after classical treatment, 4u was purified by column chromatography on silica gel with hexane/etoac as eluent (25/1). The title product was obtained as yellow oil in 62% yield and dr = 2:98. 1 H NMR (CDCl 3, 300 MHz) of the major diastereomer δ 0.88 (t, J = 7.2 Hz, 3H), 1.03 (d, J = 6.9 Hz, 3H), (m, 2H), 1.37 (s, 3H), (m, 3H), 2.36 (septet, J = 6.9 Hz, 1H), (m, 2H), 5.29 (dd, J 1 = 15.9 Hz, J 2 = 11.9 Hz, 1H), 5.76 (dd, J 1 = 15.9 Hz, J 2 = 1.2 Hz, 1H), (m, 5H). 13 C NMR (CDCl 3, 75 MHz) of the major diastereomer δ 14.7, 16.7, 17.7, 25.4, 39.9, 43.5, 44.0, 67.4, 125.6, 126.4, 128.0, 129.1, 140.8, HRMS (ESI pos) calcd. for C 16 H 24 ONa + [M+Na] + : , found: (3S*,6S*,E)-6-(iodomethyl)-2,3-dimethyl-6-phenylnon-4-en-2-ol, 4v 4v To a solution of zirconocene dichloride (496.5 mg, 1.70 mmol) in THF (45 ml) cooled to -78 C was added dropwise n-buli (1.40 M in hexane, 2.4 ml, 3.4 mmol). The resulting solution was stirred for 1 h at -78 C. A solution of alkylidenecyclopropane 2i (1.00 mmol) in THF (5 ml) was added, and the reaction mixture was slowly 11

12 warmed to 10 C. After stirring for 13 h, then the reaction was heating to 60 o C for 6 hours. After cooling the reaction to 10 o C, acetone (4 mmol) was added at 10 C and the reaction mixture was stirred for 40 min at the same temperature. Then iodine (5 mmol) was added and the mixture reaction was stirring for 3 h. An aqueous solution of HCl (1 M) was then added at 0 C and after classical treatment, 4v was purified by column chromatography on silica gel with hexane/etoac as eluent (30/1). The title product was obtained as yellow oil in 62% yield and dr = 7:93. 1 H NMR (CDCl 3, 300 MHz) of the major diastereomer δ 0.86 (t, J = 7.2 Hz, 3H), 1.07 (d, J = 7.2 Hz, 3H), 1.20 (s, 3H), 1.21 (s, 3H), 1.26 (m, 1H), 1.62 (br s, 1H), (m, 2H), (m, 1H), 3.54 (d, J = 9.9 Hz, 1H), 3.69 (d, J = 9.9 Hz, 1H), 5.45 (dd, J 1 = 15.9 Hz, J 2 = 8.7 Hz, 1H), 5.62 (dd, J 1 = 15.9 Hz, J 2 = 0.7 Hz, 1H), (m, 5H). 13 C NMR (CDCl 3, 75 MHz) of the major diastereomer δ 14.7, 15.9, 17.4, 20.1, 26.2, 27.2, 40.5, 46.9, 48.8, 72.5, 126.4, 127.0, 128.1, 131.9, 137.5, HRMS (ESI pos) calcd. for C 18 H 28 OI + [M+H] + : , found: (3S*,6R*,E)-2,3,6-trimethyl-6-phenyloct-4-en-2-ol, 4w 4w To a solution of zirconocene dichloride (496.5 mg, 1.70 mmol) in THF (45 ml) cooled to -78 C was added dropwise n-buli (1.40 M in hexane, 2.4 ml, 3.4 mmol). The resulting solution was stirred for 1 h at -78 C. A solution of alkylidenecyclopropane 2j (1.00 mmol) in THF (5 ml) was added, and the reaction mixture was slowly warmed to 10 C. After stirring for 13 h, then the reaction was heating to 65 o C for 5 hours. After cooling the reaction to 10 o C, acetone (5 mmol) was added at 10 C and the reaction mixture was stirred for 40 min at the same temperature. An aqueous solution of HCl (1 M) was then added at 10 C the mixture was stirred for 1 hour and after classical treatment, 4w was purified by column chromatography on silica gel with hexane/etoac as eluent (20/1). The title product was obtained as yellow oil in 72% yield and dr = 4:96. 1 H NMR (CDCl 3, 300 MHz) of the major diastereomer ((3S*,6R*,E)-2,3,6-trimethyl-6-phenyloct-4-en-2-ol, 4w: δ 0.74 (t, J = 9.0 Hz, 3H), 1.03 (d, J = 6.0 Hz, 3H), 1.14 (s, 3H), 1.17 (s, 3H), 1.33 (s, 3H), 1.63 (br-s, 1H), (m, 2H), (m, 1H), 5.37 (dd, J 1 = 15.0 Hz, J 2 = 6.0 Hz, 1H), 5.70 (dd, J 1 = 15.0 Hz, J 2 = 1.0 Hz, 1H), (m, 5H). 13 C NMR (CDCl 3, 75 MHz) of the major diastereomer ((3S*,6R*,E)-2,3,6-trimethyl-6-phenyloct-4-en-2-ol, 4w: δ 8.89, 15.74, 24.83, 26.59, 26.87, 33.88, 43.73, 48.46, 72.44, , , , , , HRMS (ESI pos) calcd. for C 17 H 26 ONa + [M+Na] + : , found: General procedure (procedure D) for the preparation of 1,5-dienes 6a-g from 5a-g 12

13 R 1 R 2 OMe n Cp 2 ZrC 4 H 8, Et 2 O -78 C to rt, 12 h then AcOH R 1 R 2 n H To a suspension of dicyclopentadienylzirconium dichloride (2 mmol) in ether (10 ml), was added dropwise n- butyllithium (4 mmol, 1.5M in hexanes) at -78 C. The solution was stirred 1h between -78 C and -50 C. Cyclopropanes 5 (1 mmol in 1 ml of ether) were then introduced and the solution was allowed to warm slowly to RT during 5 h. After completion of the reaction (followed by TLC), the mixture was cooled to -78 C and acetic acid (0.5 ml) was added. After warming the reaction mixture to RT, the reaction was quenched with HCl 1N and the aqueous layer was extracted twice with ether. The combined organics were washed with Na 2 CO 3, dried over MgSO 4, filtered and concentrated in vacuum. Crude mixtures were then purified by flash chromatography using pure pentane as eluent. (E)-(((3-methyl-3-vinylhept-5-en-1-yl)oxy)methyl)benzene, 6a 6a The corresponding compound was prepared following general procedure D using 5a. Purification by flash chromatography (pentane, Rf = 0.84) afforded the product as a colorless oil (190 mg, 78% yield). 1 H NMR (CDCl 3, 300 MHz) δ (ppm) 1.00 (s, 3H), 1.58 (d, J = 7.8 Hz, 3H), 1.71 (t, J = 7.6 Hz, 2H), (m, 2H), 3.48 (t, J = 7.5 Hz, 2H), 4.48 (s, 2H), 4.92 (dd, J = 17.4 Hz and 1.3 Hz, 1H), 4.99 (dd, J = 10.8 Hz and 1.3 Hz, 1H), (m, 1H), (m, 1H), 5.77 (dd, J = 17.4 Hz and 10.8 Hz, 1H), (m, 5H). 13 C NMR (CDCl 3, 100 MHz) δ (ppm) 13.1, 23.0, 38.4, 39.3, 39.6, 67.6, 73.1, 112.0, 125.9, 126.5, 127.6, 127.7, 128.5, 138.7, HRMS (ESI pos) calcd. for C 17 H 25 O + [M+H] + : , found : (E)-(((3-methyl-3-vinyl-(4-2 H 1 )hept-5-en-1-yl)oxy)methyl)benzene, 6a(D) 6a-D The corresponding compound was prepared following general procedure D using 5a. Purification by flash chromatography (pentane, Rf = 0.84) afforded the product as a colorless oil (169 mg, 69% yield). 1 H NMR (CDCl 3, 13

14 300 MHz) δ (ppm) 1.02 (s, 3H), 1.60 (d, J = 6.9 Hz, 3H), (m, 2H), (m, 1H), 3.49 (t, J = 7.4 Hz, 2H), 4.49 (s, 2H), 4.94 (dd, J = 17.4 Hz and 1.2 Hz, 1H), 5.01 (dd, J = 10.9 Hz and 1.2 Hz, 1H), (m, 1H), 5.56 (dqd, J = 11.3 Hz, 6.6 Hz and 1.2 Hz, 1H), 5.78 (dd, J = 17.4 Hz and 10.9 Hz, 1H), (m, 5H). 13 C NMR (CDCl 3, 75 MHz) δ (ppm) 13.1, 23.0, 38.0 (t, J = 19.3 Hz), 39.2, 39.6, 67.6, 73.1, 111.9, 125.9, 126.4, 127.6, 127.7, 128.5, 138.7, HRMS (ESI pos) calcd. for C 17 H 25 O + [M+H] + : , found : (E)-5-methyl-5-vinylnon-2-ene, 6b 6b The corresponding compound was prepared following general procedure D using 5b. Purification by flash chromatography (pentane, Rf = 0.97) afforded the product as a colorless oil (105 mg, 63% yield). 1 H NMR (CDCl 3, 300 MHz) δ (ppm) 0.88 (t, J = 6.9 Hz, 3H), 0.95 (s, 3H), (m, 6H), 1.60 (d, J = 6.7 Hz, 3H), (m, 2H), 4.89 (dd, J = 17.5 Hz and 1.5 Hz, 1H),4.97 (dd, J = 10.8 Hz and 1.5 Hz, 1H), (m, 1H), (m, 1H), 5.73 (dd, J = 17.5 Hz and 10.8 Hz, 1H). 13 C NMR (CDCl 3, 75 MHz) δ (ppm) 13.1, 14.3, 22.8, 23.7, 26.5, 37.9, 40.2, 40.5, 111.5, 125.4, 127.1, (E)-5-methyl-5-vinyloct-2-ene, 6c 6c The corresponding compound was prepared following general procedure D using 5c. Purification by flash chromatography (pentane, Rf = 0.97) afforded the product as a colorless oil (102 mg, 67% yield). 1 H NMR (CDCl 3, 400 MHz) δ (ppm) (m, 1H), (m, 2H), 0.93 (s, 3H), (m, 4H), 1.58 (d, J = 6.7 Hz, 3H), 2.02 (t, J = 7.8 Hz, 2H), 4.87 (d, J = 17.7 Hz, 1H), 4.95 (d, J = 10.8 Hz, 1H), 5.37 (dt, J = 10.8 Hz and 7.8 Hz, 1H), 5.51 (dq, J = 10.8 Hz and 6.7 Hz, 1H), 5.72 (dd, J = 17.7 Hz and 10.8 Hz, 1H). 13 C NMR (CDCl 3, 100 MHz) δ (ppm) 13.1, 15.0, 17.5, 22.8, 37.9, 40.3, 43.2, 111.4, 125.4, 127.1, (E)-5-phenyl-5-vinylundec-2-ene, 6d 6d 14

15 The corresponding compound was prepared following general procedure D using 5d. Purification by flash chromatography (pentane, Rf = 0.94) afforded the product as a yellowish oil (200 mg, 78% yield). 1 H NMR (CDCl 3, 300 MHz) δ (ppm) 0.86 (t, J = 6.6 Hz, 3H), (m, 2H), (m, 6H), 1.55 (d, J = 6.6 Hz, 3H), (m, 2H), 2.54 (d, J = 7.0 Hz, 2H), 5.10 (dd, J = 17.6 Hz and 1.3 Hz, 1H), 5.20 (dd, J = 10.9 Hz and 1.3 Hz, 1H), (m, 1H), (m, 1H), 5.98 (dd, J = 17.6 Hz and 10.9 Hz, 1H), (m, 5H). 13 C NMR (CDCl 3, 75 MHz) δ (ppm) 13.1, 14.2, 18.2*, 22.8, 23.7*, 23.9*, 24.2, 30.2, 30.3*, 31.9, 34.8, 37.2*, 37.5*, 37.7, 40.7*, 47.6*, 47.8, 112.7*, 112.8, 125.4*, 125.6, 125.8, 125.9, 126.7, 126.9*, 127.3*, 127.5, 128.0, 145.7, 146.1*. (*values corresponding to the minor Z-stereoisomer). HRMS (ESI pos) calcd. for C 19 H + 29 [M+H] + : , found : (E)-3-methyl-3-(phenylmethyl)hepta-1,5-diene, 6e 6e The corresponding compound was prepared following general procedure D using 5e. Purification by flash chromatography (pentane, Rf = 0.95) afforded the product as a yellowish oil (146 mg, 73% yield). 1 H NMR (CDCl 3, 300 MHz) δ (ppm) 0.94 (s, 3H), (m, 3H), 2.08 (d, J = 7.0 Hz, 2H), 2.63 (br s, 1H), 2.63 (br s, 1H), 4.81 (dd, J = 17.5 Hz and 1.3 Hz, 1H), 4.98 (dd, J = 10.8 Hz and 1.3 Hz, 1H), 5.44 (dtq, J = 11.0 Hz, 7.1 Hz and 1.5 Hz, 1H), 5.56 (dqt, J = 11.0 Hz, 6.6 Hz and 1.6 Hz, 1H), 5.81 (dd, J = 17.5 Hz and 10.8 Hz, 1H), (m, 5H). 13 C NMR (CDCl 3, 75 MHz) δ (ppm) 13.2, 22.5, 37.6, 41.3, 47.4, 112.1, 125.8, 126.0, 126.9, 127.8, 130.8, 138.7, HRMS (ESI pos) calcd. for C 15 H + 21 [M+H] + : , found : (E)-5-methyl-5-vinylundec-2-ene, 6f 6f The corresponding compound was prepared following general procedure D using 5f. Purification by flash chromatography (pentane, Rf = 0.97) afforded the product as a colourless oil (144 mg, 74% yield). 1 H NMR (CDCl 3, 300 MHz) δ (ppm) 0.86 (t, J =6.7 Hz, 3H), 0.92 (s, 3H), (m, 10H), 1.58 (d, J = 6.7 Hz, 3H), (m, 2H), 4.87 (d, J = 17.6 Hz, 1H), 4.95 (d, J = 10.8 Hz, 1H), (m, 1H), (m, 1H), 5.71 (dd, J = 17.6 Hz and 10.8 Hz, 1H). 13 C NMR (CDCl 3, 100 MHz) δ (ppm) 13.1, 14.3, 22.8, 22.8, 24.2, 30.3, 32.0, 37.8, 40.2, 40.7, 111.4, 125.4, 127.1,

16 (E)-3-ethyl-3-methylnona-1,5-diene, 6g 6g The corresponding compound was prepared following general procedure D using 5g. Purification by flash chromatography (pentane, Rf = 0.97) afforded the product as a colourless oil (103 mg, 62% yield). 1 H NMR (CDCl 3, 300 MHz) δ (ppm) (m, 3H), 0.91 (t, J = 7.8 Hz, 3H), 0.93 (s, 3H), (m, 4H), (m, 4H), 4.90 (dd, J = 17.5 Hz and 1.6 Hz, 1H), 5.00 (dd, J = 10.7 Hz and 1.6 Hz, 1H), (m, 2H), 5.71 (dd, J = 17.5 Hz and 10.7 Hz, 1H). 13 C NMR (CDCl 3, 75 MHz) δ (ppm) 8.6, 14.0, 22.2, 23.0, 29.6, 31.0, 32.9, 37.9, 11.8, 126.1, 131.5, Determination of the isomeric structures of 6: To determine if the two isomers of 6 are regioisomers of the double bond (α or β to the quaternary stereocenter), or stereoisomers (E and Z), the ozonolysis of the crude reaction mixture of 6h, followed by an in-situ reduction with NaBH 4 has been performed. The asymmetric diol 13β was the only obtained product in 53 % yield leading to the conclusion that the isomers of 6h are the two stereoisomers (E)-6h-β and (Z)-6h-β. 2-hexyl-2-methylbutane-1,4-diol, 13β 13β Title compound was prepared from the crude mixture of 6g diluted in DCM (1 ml) and MeOH (3 ml). The solution was cooled to -78 C and ozone was bubbled, warming slowly the temperature to -50 C. The reaction was followed by TLC and after total consumption of the dienes 6g (ca. 30 min), the bubbling of ozone was stopped and the reaction was warmed to 0 C. NaBH 4 (151 mg, 4.0 mmol) was then added by portions and the mixture was stirred at 16

17 0 C for 30 min. After quenching with water, the crude mixture was extracted with DCM (2 x 10 ml), dried over Na 2 SO 4, concentrated in vacuum and purified on silica gel, Rf = 0.15 (pentane/et 2 O = 4 : 1). 13β was obtained as a colourless oil (100 mg, 0.53 mmol) in 53 % over 2 steps. 1 H NMR (CDCl 3, 300 MHz) δ (ppm) 0.84 (s, 3H), 0.87 (t, J = 6.5 Hz, 3H), (m, 10H), 1.51 (dt, J = 15.1 Hz and 5.7 Hz, 1H), 1.59 (dt, J = 15.1 Hz and 5.4 Hz, 1H), 2.94 (br s, 2H), 3.33 (d, J = 11.0 Hz, 1H), 3.39 (d, J = 11.0 Hz, 1H), 3.70 (t, J = 5.6 Hz, 2H). 13 C NMR (CDCl 3, MHz) δ (ppm) 14.2, 22.3, 22.8, 23.4, 30.4, 32.0, 37.4, 37.6, 41.2, 58.6, HRMS (ESI pos) calcd. for C 11 H 25 O 2 [M+H] + : , found :

18 NMR spectra 1 H NMR (400 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 4a: 18

19 1 H NMR (400 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 4a(D) 19

20 1 H NMR (400 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 4b: 20

21 1 H NMR (400 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 4c: 21

22 1 H NMR (400 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 4d: 22

23 1 H NMR (400 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 4e: 23

24 1 H NMR (400 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 4f: 24

25 1 H NMR (400 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 4g: 25

26 1 H NMR (400 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 4h: 26

27 1 H NMR (400 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 4i: 27

28 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4j 28

29 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4k 29

30 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4l 30

31 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4m 31

32 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4n 32

33 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4o 33

34 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4p 34

35 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4q 35

36 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4r 36

37 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4s 37

38 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4t (dr = 3:1) 38

39 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4t (dr = 98:02) 39

40 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4u (dr = 92:02) 40

41 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4v (dr = 93:07) 41

42 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4w (dr = 3:1) 42

43 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 4w (dr = 96:04) 43

44 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 6a Me Ph O Me Ph O 44

45 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 6a(D) 45

46 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 6b Bu Me Bu Me 46

47 1 H NMR (400 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 6c Pr Me Pr Me 47

48 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 6d Hex Ph + Hex Ph 6d 9 : 1 6d* Hex Ph + Hex Ph 6d 9 : 1 6d* 48

49 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 6e Me Ph Me Ph 49

50 1 H NMR (400 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 6f Hex Me Hex Me 50

51 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectrum of 6g 51

52 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (100 MHz, CDCl 3 ) spectrum of 13β HO Hex Me OH HO Hex Me OH 52

53 References (31) M. S. Baird, H. H. Hussain, W. Nethercott, J. Chem. Soc. Perkin Trans. 1, 1986, (32) H. Clavier, K. Le Jeune, I. de Riggi, A. Teneglia, G. Buono, Org. Lett. 2011, 13, 308. (33) S. Simaan, A. Masarwa, P. Bertus, I. Marek, Angew. Chem. Int. Ed. 2006, 45, (34) S. Simaan, A. Masarwa, E. Zohar, A. Stanger, P. Bertus, I. Marek, Chem. Eur. J. 2009, 15, (35) S. Simaan, A. F. G. Goldberg, S. Rosset, I. Marek, Chem. Eur. J. 2010, 16, 774. (36) P.-O. Delaye, D. Didier, I. Marek, Angew. Chem. Int. Ed. 2013, 52, (37) H. Leuser, S. Perrone, F. Lion, F. Kneisel, P. Knochel, Angew. Chem. Int. Ed. 2005, 44, (38) A. D. Petrov, G.I.; Nikishin, V.D. Vorobev, Zhurnal Obshchei Khimii, 1958, 28,