Stereochemistry and mechanistic insight in the [2 k +2 i +2 i ] annulations of ketenes and imines

Stereochemistry and mechanistic insight in the [2 k +2 i +2 i ] annulations of ketenes and imines Zhanhui Yang, Wei He, Baoxiang Cheng and Jiaxi Xu* State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, Faculty of Science, Beijing University of Chemical Technology, Beijing 100029, P. R. China, Tel./ fax: +86 10 64435565; e mail: jxxu@mail.buct.edu.cn Contents 1. X ray crystal structure analysis... S2 2. 3. 1 H and 13 C NMR spectra of the [2 k +2 i +2 i ] products.... S9 1 H and 13 C NMR spectra of the [2 k +2 i ] products... S24 4. NOE spectra of the formal [2 k +2 i +2 i ] products (600 MHz).... S28 5. Computed energies of all stationary points... S42 6. Coordinates of all stationary points... S43 S1

1. X ray crystal structure analysis Fig S1. X Ray crystal structure of compound 4m (50% probability) side view Fig S2. X Ray crystal structure of compound 4m (50% probability) vertical view S2

Table 1: Crystal data and structure refinement for 4m Identification code exp_2697 Empirical formula C 21 H 19 N 3 O Formula weight 329.39 Temperature / K 97.6 Crystal system monoclinic Space group P2 1 /n a / Å, b / Å, c / Å 11.9507(10), 8.4520(5), 17.0816(14) α/, β/, γ/ 90.00, 107.700(10), 90.00 Volume / Å 3 1643.7(2) Z 4 ρ calc / mg mm -3 1.331 μ / mm -1 0.084 F(000) 696 Crystal size / mm 3 0.42 0.25 0.14 2Θ range for data collection 6 to 52 Index ranges -14 h 14, -10 k 6, -12 l 21 Reflections collected 7880 Independent reflections 3223[R(int) = 0.0343 (inf-0.9å)] Data/restraints/parameters 3223/0/226 Goodness-of-fit on F 2 1.036 Final R indexes [I>2σ (I) i.e. F o >4σ (F o )] R 1 = 0.0463, wr 2 = 0.0980 Final R indexes [all data] R 1 = 0.0651, wr 2 = 0.1084 Largest diff. peak/hole / e Å -3 0.186/-0.223 Flack Parameters N Completeness 0.999 Table 2. Fractional Atomic Coordinates ( 10 4 ) and Equivalent Isotropic Displacement Parameters (Å 2 10 3 ) for 4m. U eq is defined as 1/3 of of the trace of the orthogonalised U IJ tensor. Atom x y z U(eq) O 6408.2(10) 3773.3(13) 153.2(8) 29.4(3) N2 4084.4(11) 1819.0(14) -1900.9(8) 17.1(3) N3 6038.3(12) 2790.8(15) -1142.4(9) 23.4(3) C7 2157.4(14) 2942.7(18) -2557.3(11) 21.7(4) C2 4460.1(14) 2817.0(18) -498(1) 20.2(4) C14 5599.8(14) 1922.4(17) -2603.4(11) 20.3(4) C6 1760.9(14) 2092.3(17) -1907.8(10) 19.1(4) C13 5325.0(14) 1711.9(18) -1798.8(10) 19.1(4) C5 2566.1(14) 1361.4(17) -1241.7(10) 17.3(4) S3

C9 2173.4(15) 457.1(18) -692.3(10) 21.9(4) C1 5741.5(15) 3148.1(18) -462.2(11) 21.4(4) C3 4405.1(14) 2471.8(18) 326.2(11) 22.3(4) C4 3864.5(14) 1500.2(17) -1126.1(10) 17.8(4) C21 6787.8(17) 2846(2) -3417.9(12) 29.8(4) C18 4898.1(15) 1125.9(18) -3290.8(11) 24.0(4) C11 181.5(15) 1078.8(18) -1437.6(11) 24.4(4) C15 6553.1(15) 2807.8(18) -2663.3(12) 25.5(4) C12 561.4(15) 1953.0(18) -1994.7(11) 23.0(4) C19 5132.6(17) 1195(2) -4036.4(12) 29.6(4) N20 4325.1(13) 2133.2(17) 958.4(10) 31.5(4) C17 7265.2(15) 2991(2) -1129.2(12) 31.2(4) C10 986.6(15) 317.7(18) -790.4(11) 24.2(4) C8 3470.3(14) 3251.2(17) -2300.8(10) 19.8(4) C16 7295.1(16) 3708(2) -1932.2(12) 31.2(5) C20 6093.1(17) 2049(2) -4095.0(12) 32.0(5) Table 3 Anisotropic Displacement Parameters (Å 2 10 3 ) for 4m. The Anisotropic displacement factor exponent takes the form: -2π 2 [h 2 a* 2 U 11 +...+2hka b U 12 ] Atom U 11 U 22 U 33 U 23 U 13 U 12 O 25.3(7) 29.8(7) 30.1(7) -9.0(6) 3.8(6) -2.0(5) N2 18.7(7) 16.4(7) 18.8(7) 1.6(5) 9.6(6) 0.8(5) N3 18.1(7) 26.2(7) 27.8(8) -5.0(6) 9.6(7) -2.9(6) C7 21.8(9) 21.4(8) 22.7(9) 3.0(7) 7.7(8) 3.8(7) C2 22.6(9) 19.5(8) 19.2(9) -1.1(7) 7.2(7) 1.8(7) C14 22.8(9) 16.0(8) 26.6(9) 3.4(7) 14.0(8) 4.8(7) C6 22.0(9) 15.2(8) 21.6(9) -3.2(7) 9.0(7) -0.6(7) C13 18.6(9) 16.7(8) 23.6(9) -1.8(7) 8.9(7) -0.9(6) C5 20.8(9) 14.7(8) 17.7(9) -4.1(6) 7.8(7) -1.6(6) C9 28.4(9) 21.0(9) 17.9(9) -1.4(7) 9.3(8) -0.2(7) C1 22.4(9) 15.2(8) 25(1) -1.9(7) 4.7(8) 1.4(7) C3 20.2(9) 22.9(9) 22.6(10) -1.8(7) 4.6(8) 2.1(7) C4 20.9(9) 14.5(8) 18.9(9) 1.9(7) 7.4(7) 1.5(6) C21 31.5(10) 23.5(9) 43.1(12) 9.2(9) 24.4(10) 6.0(8) C18 27.7(10) 22.5(9) 26.5(10) 0.5(7) 15.2(8) 2.0(7) C11 19.6(9) 24.7(9) 32.6(11) -7.5(8) 13.3(8) -3.5(7) C15 26.5(10) 18.2(8) 36.3(11) 5.3(8) 16.3(9) 5.1(7) C12 22.4(9) 20.5(9) 26.1(10) -2.5(7) 7.5(8) 1.9(7) C19 36.5(11) 29(1) 27.1(10) 1.2(8) 15.2(9) 6.7(8) N20 31.7(9) 38.9(9) 23.3(9) 0.1(7) 7.5(7) 1.7(7) S4

C17 19.0(9) 37.7(11) 37.2(12) -7.3(9) 9.1(9) -3.9(8) C10 30.3(10) 23.1(9) 25.7(10) -2.8(7) 18.2(8) -4.8(7) C8 23.3(9) 17.8(8) 20.3(9) 2.2(7) 9.7(7) 1.0(7) C16 24.3(10) 28.1(10) 45.0(12) 1.1(9) 16.2(9) -3.9(8) C20 43.0(12) 29.8(10) 31.9(11) 9.7(9) 24.7(10) 12.4(9) Table 4 Bond Lengths for 4m. Atom Atom Length/ Å Atom Atom Length/Å O C1 1.229(2) C6 C5 1.392(2) N2 C13 1.4420(19) C6 C12 1.400(2) N2 C4 1.4507(19) C5 C9 1.398(2) N2 C8 1.4716(19) C5 C4 1.508(2) N3 C13 1.495(2) C9 C10 1.382(2) N3 C1 1.348(2) C3 N20 1.149(2) N3 C17 1.469(2) C21 C15 1.400(2) C7 C6 1.514(2) C21 C20 1.377(3) C7 C8 1.518(2) C18 C19 1.386(2) C2 C1 1.540(2) C11 C12 1.386(2) C2 C3 1.459(2) C11 C10 1.384(2) C2 C4 1.560(2) C15 C16 1.501(3) C14 C13 1.518(2) C19 C20 1.385(3) C14 C18 1.392(2) C17 C16 1.510(3) C14 C15 1.393(2) Table 5 Bond Angles for 4m. Atom Atom Atom Angle/ Atom Atom Atom Angle/ C13 N2 C4 110.04(13) C10 C9 C5 120.47(16) C13 N2 C8 117.20(12) O C1 N3 124.17(15) C4 N2 C8 111.91(12) O C1 C2 119.37(15) C1 N3 C13 122.94(13) N3 C1 C2 116.37(14) C1 N3 C17 118.93(14) N20 C3 C2 176.42(18) C17 N3 C13 114.87(13) N2 C4 C2 108.88(12) C6 C7 C8 113.36(14) N2 C4 C5 111.07(13) C1 C2 C4 113.42(13) C5 C4 C2 112.45(12) C3 C2 C1 109.53(14) C20 C21 C15 121.58(16) C3 C2 C4 112.10(13) C19 C18 C14 121.10(16) C18 C14 C13 117.82(14) C10 C11 C12 120.21(16) C18 C14 C15 119.64(16) C14 C15 C21 118.50(17) C15 C14 C13 122.46(16) C14 C15 C16 120.07(16) C5 C6 C7 121.15(14) C21 C15 C16 121.42(15) S5

C5 C6 C12 118.72(15) C11 C12 C6 120.69(16) C12 C6 C7 120.04(15) C20 C19 C18 119.47(18) N2 C13 N3 112.54(12) N3 C17 C16 109.35(15) N2 C13 C14 112.38(14) C9 C10 C11 119.74(16) N3 C13 C14 112.13(13) N2 C8 C7 108.58(12) C6 C5 C9 120.13(15) C15 C16 C17 112.40(14) C6 C5 C4 120.05(14) C21 C20 C19 119.69(17) C9 C5 C4 119.79(15) Table 6 Torsion Angles for 4m. A B C D Angle/ N3 C17 C16 C15-52.43(19) C7 C6 C5 C9-173.92(14) C7 C6 C5 C4 4.1(2) C7 C6 C12 C11 175.20(15) C14 C18 C19 C20 1.1(2) C14 C15 C16 C17 26.0(2) C6 C7 C8 N2 43.24(18) C6 C5 C9 C10-1.9(2) C6 C5 C4 N2-24.26(19) C6 C5 C4 C2 98.05(17) C13 N2 C4 C2 64.21(15) C13 N2 C4 C5-171.44(12) C13 N2 C8 C7 164.67(13) C13 N3 C1 O 165.52(15) C13 N3 C1 C2-17.9(2) C13 N3 C17 C16 61.37(18) C13 C14 C18 C19-176.65(15) C13 C14 C15 C21 175.55(14) C13 C14 C15 C16-5.1(2) C5 C6 C12 C11-1.2(2) C5 C9 C10 C11 0.0(2) C9 C5 C4 N2 153.79(13) C9 C5 C4 C2-83.91(17) C1 N3 C13 N2 33.2(2) C1 N3 C13 C14 161.09(14) C1 N3 C17 C16-138.42(16) C1 C2 C3 N20-133(3) C1 C2 C4 N2-48.08(17) C1 C2 C4 C5-171.62(13) S6

C3 C2 C1 O -32.1(2) C3 C2 C1 N3 151.12(14) C3 C2 C4 N2-172.76(13) C3 C2 C4 C5 63.70(17) C4 N2 C13 N3-56.24(16) C4 N2 C13 C14 176.02(12) C4 N2 C8 C7-66.86(16) C4 C2 C1 O -158.14(14) C4 C2 C1 N3 25.06(19) C4 C2 C3 N20-6(3) C4 C5 C9 C10-179.95(14) C21 C15 C16 C17-154.71(16) C18 C14 C13 N2-44.53(18) C18 C14 C13 N3-172.48(13) C18 C14 C15 C21-1.1(2) C18 C14 C15 C16 178.28(15) C18 C19 C20 C21-1.4(3) C15 C14 C13 N2 138.80(15) C15 C14 C13 N3 10.8(2) C15 C14 C18 C19 0.1(2) C15 C21 C20 C19 0.4(3) C12 C6 C5 C9 2.5(2) C12 C6 C5 C4-179.47(14) C12 C11 C10 C9 1.2(2) C17 N3 C13 N2-167.44(13) C17 N3 C13 C14-39.57(18) C17 N3 C1 O 7.0(2) C17 N3 C1 C2-176.39(14) C10 C11 C12 C6-0.6(2) C8 N2 C13 N3 73.12(17) C8 N2 C13 C14-54.62(17) C8 N2 C4 C2-67.95(16) C8 N2 C4 C5 56.40(16) C8 C7 C6 C5-14.1(2) C8 C7 C6 C12 169.54(13) C20 C21 C15 C14 0.8(2) C20 C21 C15 C16-178.53(16) S7

Table 7 Hydrogen Atom Coordinates (Å 10 4 ) and Isotropic Displacement Parameters (Å 2 10 3 ) for 4m. Atom x y z U(eq) H7A 1746 3945-2681 26 H7B 1941 2314-3056 26 H2 4017 3795-679 24 H13 5562 631-1613 23 H9 2715-55 -258 26 H4 4234 487-916 21 H21 7428 3423-3463 36 H18 4261 537-3249 29 H11-617 1003-1499 29 H12 14 2452-2431 28 H19 4649 673-4494 36 H17A 7658 1973-1050 37 H17B 7673 3676-677 37 H10 730-285 -423 29 H8A 3712 3509-2779 24 H8B 3664 4137-1923 24 H16A 7018 4792-1964 37 H16B 8100 3728-1947 37 H20 6268 2085-4589 38 Experimental Single crystals of C 21 H 19 N 3 O [4m] were recrystallized from [acetone] mounted in inert oil and transferred to the cold gas stream of the diffractometer. Crystal structure determination of [4m] Crystal Data. C 21 H 19 N 3 O, M =329.39, monoclinic, a = 11.9507(10) Å, b = 8.4520(5) Å, c = 17.0816(14) Å, β = 107.700(10), U = 1643.7(2) Å 3, T = 97.6, space group P2 1 /n (no. 14), Z = 4, μ(mo Kα) = 0.084, 7880 reflections measured, 3223 unique (R int = 0.0343) which were used in all calculations. The final wr(f 2 ) was 0.1084 (all data). S8

2. 1 H and 13 C NMR spectra of the [2 k +2 i +2 i ] products. Benzyl ((rel(4bs,5s,13br) 6 oxo 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoquinoli n 5 yl)methyl)carbamate (4a) S9

2 ((rel(4bs,5s,13br) 6 Oxo 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoquino lin 5 yl)methyl)isoindoline 1,3 dione (4b) S10

(4b,5) cis (4b,13b) syn 5 ethoxy 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diiso quinolin 6 one (4c) S11

(4b,5) cis (4b,13b) syn 5 (benzyloxy) 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a'] diisoquinolin 6 one (4e) S12

rel(4br,5r,13br) 5 (Phenoxy) 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoqu inolin 6 one (4fb) S13

rel(4br,5s,13br) 5 (Phenoxy) 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoqu inolin 6 one (4fa) S14

rel(4br,5r,13br) 5 (4 Nitrophenoxy) 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a'] diisoquinolin 6 one (4gb) S15

rel(4br,5r,13bs) 5 (4 Nitrophenoxy) 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a'] diisoquinolin 6 one (4gc) S16

rel(4bs,5r,13br) 5 (Phenyl) 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoquin olin 6 one (4h) S17

ethyl rel(4br,5s,13bs) 4b,5,9,13b,15,16 Hexahydro 6 oxo 6H,8H pyrimido[2,1 a:4,3 a']diisoquinolin e 5 carboxylate (4i) S18

rel(4br,5r,13bs) N Methyl 4b,5,9,13b,15,16 hexahydro 6 oxo 6H,8H pyrimido[2,1 a:4,3 a']diis oquinoline 5 carboxamide (4j) S19

rel(4br,5r,13bs) N Methyl N phenyl 4b,5,9,13b,15,16 hexahydro 6 oxo 6H,8H pyrimido[2,1 a: 4,3 a']diisoquinoline 5 carboxamide (4ka) S20

(4bR,5R,13bS) N methyl 6 oxo N phenyl 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoquinoline 5 carboxamide (Two inseparable rotamers) Minor rotamer:4kc S21

(4bR,5R,13bS) N methyl 6 oxo N phenyl 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoquinoline 5 carboxamide (Two inseparable rotamers) Major rotamer: 4kb S22

(4bR,5R,13bS) 6 oxo 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoquinoline 5 carbonitrile (4m) S23

3. 1 H and 13 C NMR spectra of the [2 k +2 i ] products. trans 1 Ethoxy 1,4,5,9b tetrahydro 2H azeto[2,1 a]isoquinolin 2 one (5c) S24

trans-1-isopropoxy-1,4,5,9b-tetrahydro-2h-azeto[2,1-a]isoquinolin-2-one (5d) S25

trans 1 (benzyloxy) 1,4,5,9b tetrahydro 2H azeto[2,1 a]isoquinolin 2 one (5e) S26

trans 1 Phenoxy 1,4,5,9b tetrahydro 2H azeto[2,1 a]isoquinolin 2 one (5f) S27

4. NOE spectra of the formal [2 k +2 i +2 i ] products (600 MHz). Benzyl ((rel(4bs,5s,13br) 6 oxo 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoquinoli n 5 yl)methyl)carbamate (4a) S28

2 ((rel(4bs,5s,13br) 6 Oxo 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoquino lin 5 yl)methyl)isoindoline 1,3 dione (4b) S29

S30

rel(4br,5s,13br) 5 Ethoxy 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoquino lin 6 one (4c) S31

rel(4br,5s,13br) 5 (Benzyloxy) 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoq uinolin 6 one (4e) S32

rel(4br,5s,13br) 5 (Phenoxy) 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoqu inolin 6 one (4fa) S33

rel(4br,5r,13br) 5 (Phenoxy) 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoqu inolin 6 one (4fb) S34

rel(4br,5r,13br) 5 (4 Nitrophenoxy) 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a'] diisoquinolin 6 one (4gb) S35

rel(4bs,5r,13br) 5 (Phenyl) 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a:4,3 a']diisoquin olin 6 one (4h) S36

ethyl rel(4br,5s,13bs) 4b,5,9,13b,15,16 Hexahydro 6 oxo 6H,8H pyrimido[2,1 a:4,3 a']diisoquinolin e 5 carboxylate (4i) S37

rel(4br,5r,13bs) N Methyl 4b,5,9,13b,15,16 hexahydro 6 oxo 6H,8H pyrimido[2,1 a:4,3 a']diis oquinoline 5 carboxamide (4j) S38

rel(4br,5r,13bs) N Methyl N phenyl 4b,5,9,13b,15,16 hexahydro 6 oxo 6H,8H pyrimido[2,1 a: 4,3 a']diisoquinoline 5 carboxamide (4ka) S39

rel(4br,5r,13bs) N Methyl 6 oxo N phenyl 4b,5,9,13b,15,16 hexahydro 6H,8H pyrimido[2,1 a: 4,3 a']diisoquinoline 5 carboxamide (Two inseparable rotamers) S40

rel(4br,5r,13bs) 4b,5,9,13b,15,16 Hexahydro 6 oxo 6H,8H pyrimido[2,1 a:4,3 a']diisoquinolin e 5 carbonitrile (4m) S41

5. Computed energies of all stationary points m06 2x gd3/6 311+ +g(d,p) b3lyp gd3/6 3 1g(d) PhO(smd,CH 2 Cl 2 ) E TCGqhc G/(kcal/mol) ΔG sol /(kcal/ mol) intermediate 6f 861.8914164 0.240604 861.6508124 imine 1a 403.0627272 0.127179 402.9355482 sum of 6f and 1a 1264.954144 0.367783 1264.586361 0 exo TS2 f 1264.947349 0.394414 1264.552935 20.9748530 8 endo TS1 f 1264.954809 0.394495 1264.560314 16.3444818 9 endo 4fa 1265.046789 0.402286 1264.644503 36.4851583 1 exo 4fa 1265.044828 0.401348 1264.64348 35.8428955 5 4 NO 2 PhO (smd,ch 2 Cl 2 ) intermediate 6g 1066.388594 0.240237 1066.148357 imine 1a 403.0627272 0.127179 402.9355482 sum of 6g and 1a 1469.451322 0.367416 1469.083906 0 exo TS2 g 1469.444242 0.3880055 1469.056236 17.3628597 1 endo TS1 g 1469.446869 0.394601 1469.052268 19.8529197 9 endo 4gc 1469.54235 0.401751 1469.140599 35.5754903 2 exo 4gc 1469.539669 0.40148 1469.138189 34.0634171 2 Ph endo (2,4) cis (4,5) cis 4 h epi endo (2,4) cis (4,5) t rans 4h 1189.834297 0.398627 1189.43567 3.19133388 2 1189.838578 0.397822 1189.440756 0 S42

6. Coordinates of all stationary points endo product: (2,4) cis (4,5) cis 4h O 0.78762500 2.20076400 2.57487500 N 1.54147300 0.27175600 1.65565100 C 0.81051800 0.91020400 1.31618400 H 1.50373800 1.23210500 2.09761600 C 2.51460800 0.78154300 0.29432400 C 1.41895500 0.90822700 0.76491100 H 1.64547800 1.78859300 1.39681700 C 0.57116400 1.19430300 1.89476900 C 4.88063700 0.42417800 0.67391800 H 5.88080100 0.25648500 0.28096700 C 2.29448200 0.78776900 1.67287200 H 1.28518800 0.88534300 2.05805600 C 3.81130900 0.57982400 0.21020400 C 3.37152900 0.64020600 2.55223200 H 3.19561400 0.64972800 3.62462900 C 4.66494000 0.46886400 2.05438100 H 5.50178900 0.35158600 2.73788100 N 0.08648100 1.04911300 0.19574900 C 1.34911000 2.38630900 1.23005400 H 1.57351800 3.39844300 1.58711100 C 2.54857900 1.81310600 0.51134900 C 2.36186900 1.00829300 0.62384500 C 3.48515700 0.57461400 1.34450800 H 3.34937700 0.01876000 2.24487400 C 0.97225700 0.61890300 1.11402000 H 0.83348800 1.08782400 2.10836500 C 4.96201200 1.65560300 0.22940700 S43

H 5.96441100 1.90487100 0.56767300 C 3.85116900 2.12062700 0.92941200 H 3.98618500 2.74533200 1.80998800 C 4.77586900 0.88739000 0.92395000 H 5.63150700 0.53516500 1.49404600 H 1.10266300 1.77913800 2.11164200 C 0.14342700 2.41359900 0.29842200 H 0.74397400 2.75906300 0.83224900 H 0.31519600 3.11586100 0.53793700 C 3.92912500 0.45465900 1.70767400 H 4.92144300 0.10038800 2.00263700 H 3.78231700 1.43155600 2.18850200 C 2.87624200 0.53910600 2.22668900 H 3.16090000 1.55963300 1.95127100 H 2.81208000 0.50185400 3.31971500 C 1.08531400 1.73189700 0.06522400 C 0.12120900 1.88442400 0.94187800 C 2.33669400 2.33821000 0.11103300 C 0.40676700 2.60851800 2.10039700 H 0.85882500 1.43731900 0.82289900 C 2.62676700 3.06102200 1.27044200 H 3.09321400 2.23526900 0.66193200 C 1.66245400 3.19715200 2.27167800 H 0.35573100 2.71237800 2.86847400 H 3.60516100 3.52009700 1.38784800 H 1.88529000 3.76061000 3.17416800 SCF Done: 1189.83429698 hartree zero point correction: 0.445488 hartree quasiharmonic free energy correction: 0.398627 hartree S44

epi endo product: (2,4) cis (4,5) trans 4h O 0.30770300 2.78981700 1.45316600 N 1.24715300 1.54463500 0.34593100 C 1.10704700 0.72601100 0.54119700 C 3.04000100 0.06989700 0.57759600 C 1.55351300 0.40980700 0.56105000 C 0.01770300 1.78652900 0.79791300 C 5.33344600 0.36930700 0.12167300 C 3.45149400 0.97340400 1.41914300 C 3.98641400 0.75201800 0.20063500 C 4.79077800 1.34899100 1.48569100 C 5.73817900 0.67364000 0.70873200 N 0.74994600 0.75786000 0.25609700 C 0.37417000 2.79184400 1.02910200 C 1.05677500 2.76228800 0.53151900 C 1.53402000 1.67245600 0.21682000 C 2.83004300 1.71599500 0.75134400 C 0.67173100 0.43877500 0.41802700 C 3.19786100 3.88667500 0.23858000 C 1.90276100 3.85794600 0.75386600 C 3.66099300 2.81270900 0.52713700 C 1.03009600 1.41222700 1.03122700 C 3.54749800 1.88765700 1.09588200 C 2.29022700 2.55256400 0.54343700 C 2.38813500 1.39287300 0.07985100 C 2.40956300 2.14509700 1.10437300 C 3.58354000 1.22040400 0.78644000 S45

C 3.59789800 2.70633600 1.57221900 C 4.77652500 1.77992300 0.32124100 C 4.78832900 2.52198800 0.86157200 H 1.28936000 0.29643700 1.53301400 H 1.27328400 0.71169500 1.58114500 H 6.06802100 0.90306900 0.72078300 H 2.70536500 1.49803700 2.00954000 H 5.09551100 2.16117500 2.14023100 H 6.78707600 0.95448800 0.75690400 H 0.95628800 3.45367700 0.37271100 H 0.41971000 3.22784800 2.03438900 H 3.18670700 0.88143400 1.34748900 H 0.79913200 0.08437600 1.44790700 H 3.83855400 4.74483900 0.42508600 H 1.53190900 4.69959100 1.33553900 H 4.66267600 2.82883000 0.94849300 H 0.67615200 0.81888400 1.88867300 H 2.11187900 1.51669100 1.13984000 H 4.34947700 2.62889600 1.19001600 H 3.33647600 1.51273800 2.10710500 H 2.51092100 3.04336300 0.41511900 H 1.89764000 3.30347900 1.22798100 H 1.48702400 2.29463900 1.66164900 H 3.58107500 0.63351800 1.70152500 H 3.59547700 3.28729800 2.49101300 H 5.69584900 1.63202900 0.88223400 H 5.71546600 2.95598200 1.22671800 SCF Done: 1189.83857769 hartree zero point correction: 0.444858 hartree quasiharmonic free energy correction: 0.397822 hartree S46

Imine 1a: N 2.36304300 0.89411400 0.02740200 C 1.28294800 1.37250800 0.28205500 H 1.28240000 2.38899900 0.12652400 C 0.06204200 0.70950400 0.10022600 C 0.07956800 0.69940400 0.08528200 C 1.29447500 1.39093500 0.00452400 H 1.29241200 2.47882000 0.00896300 C 1.20663400 1.41220400 0.16171700 H 1.16278500 2.48478900 0.37463400 C 2.47858400 0.71204300 0.09173000 H 3.41121600 1.26526700 0.16604100 C 1.26744600 1.40527000 0.01145600 H 1.26120200 2.49283300 0.02288800 C 2.49486900 0.68612800 0.09715900 H 3.43739700 1.22134100 0.17273500 H 1.48929600 1.46212300 1.35948100 C 2.39223300 0.53818600 0.36964900 H 2.32313400 0.60808200 1.46619500 H 3.37432600 0.93339200 0.09077100 SCF Done: 403.062727185 hartree zero point correction: 0.159110 hartree quasiharmonic free energy correction: 0.127179 hartree S47

Intermediate 6f: C 1.38720500 0.34391100 0.45668600 C 0.32104600 1.01470600 0.09342300 N 0.98948100 0.29040200 0.06158700 C 2.06354200 0.96284000 0.25735400 O 0.26367800 2.12936600 0.65515300 O 2.60492700 1.01040900 0.48745700 C 3.74108000 0.30861700 0.18777600 C 3.74172000 0.93485700 0.45759800 C 4.95843000 1.56905600 0.72382900 C 6.16968700 0.97696500 0.36083800 C 6.15785700 0.27072900 0.27447900 C 4.95330100 0.91321900 0.55077800 C 3.39863300 0.43289800 0.14787900 C 3.57594200 0.95659000 0.03731700 C 2.33251000 1.80755200 0.02297800 C 1.13564800 1.07524800 0.63015700 C 4.51177100 1.28838600 0.23826100 C 5.79612500 0.76583400 0.11882800 C 5.97145500 0.60904200 0.07579800 C 4.86646700 1.46588300 0.14627800 H 1.35716800 0.59825100 0.98578600 H 1.88087300 1.97710000 0.59912400 H 2.80314400 1.38619000 0.76166700 S48

H 4.95305400 2.53299400 1.22686700 H 7.11070600 1.47774500 0.57069600 H 7.09285600 0.74657200 0.55947700 H 4.92716600 1.87916800 1.04674900 H 2.48387700 2.74376900 0.56918100 H 2.09799700 2.07594900 1.01694900 H 0.22678600 1.63243600 0.41754800 H 1.24354300 0.96686300 1.71480900 H 4.35768000 2.35352800 0.38880600 H 6.65851300 1.42306200 0.17821000 H 6.97371600 1.01799500 0.16909100 H 5.01299500 2.53393500 0.28470600 SCF Done: 861.891416413 hartree zero point correction: 0.282236 hartree quasiharmonic free energy correction: 0.240604 hartree S49

endo TS1 f: O 0.17990700 0.83559800 2.31370400 N 1.56794800 1.39824900 0.87381400 C 0.52233600 2.53097600 0.64593700 H 0.07166000 3.18342200 0.09369500 C 3.11488700 0.40670100 0.72927600 C 1.74170800 0.78198300 0.30896700 H 1.06377600 1.10245700 1.09375500 C 0.15624600 1.58164700 1.36154500 C 5.50001800 0.41078700 0.35214000 H 6.35367100 0.67709600 0.26647700 C 3.31105200 0.27463600 1.93871300 H 2.44832100 0.54585600 2.54143800 C 4.21276700 0.75643300 0.07554300 C 4.59563700 0.61479500 2.35199800 H 4.74446300 1.14603500 3.28779300 C 5.69309800 0.27006700 1.55389200 H 6.69877300 0.53602800 1.86849400 N 0.82472100 0.91892700 0.19176300 C 0.59257400 3.20909700 0.75100700 H 0.79193800 3.79814300 1.65192600 C 0.89191200 3.10510700 0.48747800 C 1.34036500 2.00109700 0.26776800 C 2.69528100 1.86139200 0.60232200 S50

H 3.02275300 0.99627700 1.17217400 C 0.36270300 0.99849300 0.67573900 H 0.65928200 0.25241900 1.41184500 C 3.17374400 3.91392600 0.57522600 H 3.88830100 4.66034800 0.91183900 C 1.82015100 4.05807100 0.90111500 H 1.48801900 4.91370100 1.48367000 C 3.61313400 2.81842800 0.17499100 H 4.66547200 2.70963700 0.42081500 H 1.07015400 3.73360400 0.08967800 C 1.21574800 1.81956300 0.90122200 H 0.87957800 1.32692100 1.82261700 H 2.30682900 1.87817100 0.91307600 C 3.96720800 1.52857300 1.35030900 H 4.73775100 1.29805700 2.09397800 O 1.88216300 2.75367600 0.94387800 C 2.82171100 2.32493700 0.05381300 C 4.14776300 2.29211200 0.51409600 C 2.54120200 1.95440200 1.26960400 C 5.17323700 1.87889900 0.33328200 H 4.34661600 2.58174700 1.54212800 C 3.58047500 1.54733400 2.11196500 H 1.51849300 1.98257700 1.62698800 C 4.89899400 1.50045900 1.65353800 H 6.19365700 1.84800400 0.04097200 H 3.35058800 1.26550900 3.13712700 H 5.70124900 1.17982600 2.31239800 H 4.03677800 2.60527600 1.13950200 C 2.58711200 1.21711600 1.92268600 H 2.55481400 0.19843600 2.32330900 H 2.33685200 1.89914700 2.73699300 imaginary frequencies: 217 cm** 1 SCF Done: 1264.95480903 hartree zero point correction: 0.443645 hartree quasiharmonic free energy correction: 0.394495 hartree S51

exo TS2 f: O 0.37494700 3.17696500 0.92975700 N 1.81247200 1.55989200 0.08567800 C 0.57093800 1.31820800 0.19678300 H 0.48241100 0.57857100 0.97362000 C 3.43823600 0.09005300 0.66421000 C 2.06614700 0.40361400 0.55235900 H 1.38790100 0.12280900 1.34667100 C 0.48243200 2.12575800 0.26771300 C 5.66807400 0.22895800 0.25721500 H 6.38919400 0.04425200 1.02364600 C 3.81958000 0.92460000 1.72432100 H 3.09828000 1.17849400 2.49668500 C 4.36665600 0.26147200 0.33413200 C 5.12556300 1.41077800 1.79127400 H 5.42373900 2.05258300 2.61540300 C 2.89916800 2.19929000 0.86509200 H 2.42151300 2.78379000 1.64940000 C 6.04779800 1.06389400 0.80003100 H 7.06670800 1.43812300 0.85161100 N 1.13154300 1.08632600 0.63780900 C 0.64817400 2.29841900 0.70588700 H 0.85700400 3.27431700 1.15877600 C 1.63104600 1.98690200 0.39689300 S52

C 1.21420500 1.06799600 1.38171700 C 2.09641800 0.67772900 2.39856600 H 1.76530000 0.03918700 3.14600600 C 0.14099600 0.51166800 1.29480400 H 0.41083200 0.24890200 2.02468600 C 3.80540500 2.10849600 1.46506400 H 4.81394500 2.51238700 1.49166500 C 2.92676300 2.49793200 0.44763400 H 3.25627300 3.19758500 0.31718700 C 3.38796900 1.20140600 2.44373900 H 4.07055700 0.89600600 3.23228900 H 0.76400100 1.55264200 1.50628700 C 0.79110700 2.26500300 0.17000600 H 0.96254800 3.14623400 0.46573600 H 1.50878000 2.33641500 0.99437900 C 3.85804800 1.15664800 1.43456000 H 3.43089300 2.89160100 0.20106700 H 4.68181100 1.66559300 1.94506800 H 3.33065100 0.55046100 2.18493200 O 1.84644300 1.74576500 0.09857600 C 2.89993400 1.29733900 0.65607400 C 4.14121900 1.25089800 0.00922600 C 2.79563400 0.93529000 2.00640100 C 5.27004600 0.82625300 0.70556800 H 4.19389700 1.53235200 1.03715400 C 3.93588400 0.50287200 2.68901300 H 1.84666200 1.00934300 2.52691200 C 5.17458800 0.44131900 2.04775300 H 6.22748800 0.78560300 0.19259100 H 3.84975400 0.22241000 3.73585600 H 6.05519200 0.10236200 2.58607900 imaginary frequencies: 274 cm** 1 SCF Done: 1264.94734907 hartree zero point correction: 0.443389 hartree quasiharmonic free energy correction: 0.394414 hartree S53

endo product (2,4) cis (4,5) cis 4fa: O 0.12152000 3.09761600 0.56665800 N 1.57193800 1.56479700 0.53449800 C 0.78608800 0.81034900 0.78059100 H 1.46104400 1.10932900 1.58779200 C 3.42633400 0.09832800 0.30476500 C 2.03248500 0.18361800 0.85436000 H 2.08940200 0.11172800 1.95106900 C 0.26484900 1.92772500 0.63879000 C 5.44065600 0.50026700 0.88791200 H 6.01394900 1.23687500 1.44647300 C 3.97529200 1.36274500 0.56162800 H 3.38949600 2.08633600 1.12168600 C 4.16393200 0.84695300 0.42252700 C 5.24174800 1.69843200 0.09003600 H 5.65360200 2.68325200 0.29343100 C 5.97885600 0.76088800 0.64141700 H 6.97060000 1.01056300 1.00923300 N 1.08101300 0.82535800 0.43821300 C 0.19000300 2.35582600 1.22993800 H 0.07246000 2.46177600 2.28937800 C 1.05316600 2.47653200 0.37136900 C 1.21396700 1.67536900 0.76953800 C 2.35181400 1.82255200 1.57151800 S54

H 2.46920700 1.18989800 2.44894100 C 0.20508000 0.59391700 1.10004400 H 0.00865300 0.60049200 2.18081700 C 3.18400300 3.55362100 0.11243800 H 3.94720600 4.28089400 0.15239400 C 2.04872200 3.41215300 0.68563800 H 1.92868100 4.03229300 1.57167000 C 3.33582200 2.75646600 1.25074700 H 4.21544700 2.85896200 1.88054700 H 0.86764500 3.18659100 0.98858700 C 0.93784600 1.04014400 1.01225200 H 0.41368500 0.21036100 1.50471900 H 1.93561500 1.10777800 1.45084900 C 3.58462800 2.21865200 0.68098600 H 3.06181900 2.23404700 1.64722300 O 1.50891800 0.76698900 0.46160700 C 2.82828800 1.16086400 0.47433700 C 3.26538300 2.35050400 0.11777300 C 3.72574900 0.32968100 1.15255600 C 4.61732900 2.69459600 0.03715100 H 2.54171500 2.99525000 0.60536400 C 5.07004300 0.69271100 1.23703800 H 3.35860000 0.59513100 1.58606400 C 5.52346900 1.87291100 0.63865400 H 4.95853200 3.61944000 0.49567100 H 5.76704800 0.04314100 1.76043400 H 6.57239900 2.14968500 0.70055800 H 4.38559200 2.96456800 0.73725600 C 2.60031700 2.60159000 0.41964300 H 2.09941400 3.54450500 0.20354900 H 3.12487300 2.70214100 1.38020900 SCF Done: 1265.04482784 hartree zero point correction: 0.449213 hartree quasiharmonic free energy correction: 0.401348 hartree S55

exo product (2,4) trans (4,5) trans 4fa: O 0.07959300 2.83807800 0.67527100 N 1.59233500 1.26060300 1.32669700 C 0.58904100 0.54281800 0.39898400 H 1.24400100 0.35924900 1.25902600 C 3.12028100 0.07723700 0.07125400 C 2.14934200 0.10270900 1.11805700 H 2.72494600 0.32831600 2.02311600 C 0.39929200 1.65478100 0.79205400 C 4.62881800 1.09953600 1.54848700 H 5.09030900 2.03068100 1.87062700 C 3.44929800 1.27418300 0.72007900 H 2.97450700 2.19292500 0.38970600 C 3.71910100 1.12900800 0.48200200 C 4.35239400 1.28714200 1.78185400 H 4.58907100 2.22257600 2.28209400 C 2.64083200 2.26867000 1.50392800 H 2.18541400 3.19978400 1.84193800 C 4.94528300 0.09218500 2.19887300 H 5.65299800 0.08913500 3.02394400 N 1.13807600 1.11926400 0.99965000 C 0.12735600 2.93518800 2.02153500 H 0.63797100 3.70839600 1.86723800 C 1.03393700 2.90181100 0.80837500 S56

C 0.87878000 1.91335900 0.17804900 C 1.67988500 1.95300200 1.32855700 H 1.54393700 1.19376000 2.09162300 C 0.11708500 0.78314200 0.00412900 H 0.62724300 0.59644100 0.94758800 C 2.81019300 3.92200600 0.50951300 H 3.56005300 4.69994500 0.62833100 C 2.00432900 3.89769400 0.62741600 H 2.12274900 4.66233500 1.39251800 C 2.64243500 2.94647200 1.49704000 H 3.25610200 2.96029200 2.39390800 H 0.69540900 3.22750900 2.91280700 C 0.57138000 1.59959100 2.26823300 H 0.13053700 0.87928300 2.71838700 H 1.39295100 1.73238400 2.97846000 C 3.38281700 2.45570100 0.17690700 H 3.31881900 1.90611700 2.28445500 H 2.74484300 3.04109300 0.49864000 H 4.29623500 3.04178900 0.33432700 O 1.36077600 0.96672900 0.71964100 C 2.61568200 1.48868200 0.53020400 C 3.52026300 1.29536300 1.58245000 C 3.00749200 2.19544900 0.61264000 C 4.81518600 1.80218700 1.48759900 H 3.19486400 0.74235100 2.45819400 C 4.31287400 2.68763700 0.69870000 H 2.29242700 2.39296100 1.40196300 C 5.22238800 2.49618900 0.34332400 H 5.51078600 1.64512800 2.30800000 H 4.61071500 3.23829900 1.58750000 H 6.23363300 2.88622400 0.26860500 SCF Done: 1265.04678935 hartree zero point correction: 0.449918 hartree quasiharmonic free energy correction: 0.402286 hartree S57

Imine 1a: N 2.36304300 0.89411400 0.02740200 C 1.28294800 1.37250800 0.28205500 H 1.28240000 2.38899900 0.12652400 C 0.06204200 0.70950400 0.10022600 C 0.07956800 0.69940400 0.08528200 C 1.29447500 1.39093500 0.00452400 H 1.29241200 2.47882000 0.00896300 C 1.20663400 1.41220400 0.16171700 H 1.16278500 2.48478900 0.37463400 C 2.47858400 0.71204300 0.09173000 H 3.41121600 1.26526700 0.16604100 C 1.26744600 1.40527000 0.01145600 H 1.26120200 2.49283300 0.02288800 C 2.49486900 0.68612800 0.09715900 H 3.43739700 1.22134100 0.17273500 H 1.48929600 1.46212300 1.35948100 C 2.39223300 0.53818600 0.36964900 H 2.32313400 0.60808200 1.46619500 H 3.37432600 0.93339200 0.09077100 SCF Done: 403.062727185 hartree zero point correction: 0.159110 hartree quasiharmonic free energy correction: 0.127179 hartree S58

6g: C 0.19095200 1.89220800 0.19018000 C 0.44973500 0.90822400 0.52291100 N 1.89257500 0.71036000 0.14018400 C 2.47195800 0.36532600 0.59739600 O 0.00653200 0.11199400 1.37041300 O 1.52172800 2.20047400 0.10862300 H 0.23961800 2.57824300 0.90170800 C 3.83566900 0.72172500 0.30395300 C 4.69348300 0.24650000 0.26420300 C 4.13044900 1.63169700 0.45038500 C 2.63932400 1.60108200 0.78625500 C 4.30685100 2.01437100 0.59597700 C 5.62419600 2.35061100 0.30023700 C 6.47242100 1.39454100 0.27040900 C 6.01135700 0.10146000 0.54471400 H 1.84025100 0.99929200 1.21299900 C 2.49735600 1.26756200 0.01150800 C 2.33264900 0.00854200 0.59353100 C 3.41071300 0.85855300 0.67573300 C 4.65077500 0.47501800 0.15168800 C 4.82602800 0.77687800 0.45254900 C 3.75015200 1.64413800 0.53011300 N 5.77210400 1.38856200 0.23512200 S59

O 5.59711400 2.49268700 0.76814000 O 6.86243000 1.02901100 0.22922100 H 4.65545900 2.17126800 1.24451600 H 4.27854000 2.20189700 0.47771600 H 2.22911500 2.60424900 0.69972300 H 2.46437800 1.23030200 1.80192400 H 3.63298900 2.74221700 1.03968200 H 5.99242600 3.34942800 0.51421000 H 7.50176300 1.65560800 0.50029600 H 6.68244200 0.63635600 0.97633700 H 1.36994900 0.27169200 1.00093300 H 3.30263100 1.82971700 1.14337800 H 5.79447400 1.05506800 0.84975200 H 3.85170500 2.62045000 0.99279300 SCF Done: 1066.38859446 hartree zero point correction: 0.284981 hartree quasiharmonic free energy correction: 0.240237 hartree S60

endo TS1 g: O 0.39347600 0.71261500 0.96450100 N 1.57062200 1.42315800 0.08086700 C 0.34988600 0.84260500 1.41012300 C 3.94218600 1.11072200 0.54081900 C 2.52371800 0.75338200 0.76463500 C 0.15667200 0.95455900 0.13740000 C 5.67006400 2.03719800 0.86679700 C 4.89659400 0.81974200 1.52362300 C 4.32438400 1.72011800 0.66688100 C 6.23630900 1.14098400 1.31366000 C 6.62141500 1.75061500 0.11535500 N 2.32664000 1.07373200 0.21812800 C 2.08897500 2.81249200 1.54653300 C 0.82576800 3.27147300 0.85763500 C 0.55580000 2.72577600 0.41438200 C 0.57122300 3.12829200 1.14644100 C 1.45048200 1.70231900 0.93203500 C 1.17979400 4.61371300 0.65628900 C 0.04991900 4.21990000 1.38208200 C 1.44344400 4.06990500 0.60558700 C 2.37256700 1.34137500 1.22907800 C 3.25390300 1.99008000 1.69720700 O 1.55832100 0.15334200 1.63792700 S61

C 2.70631600 0.55809000 1.06084700 C 3.79446100 0.33058400 1.17113700 C 2.87142300 1.79407600 0.40581600 C 5.02674100 0.00366000 0.63935500 C 4.10640200 2.13173800 0.12153700 C 5.17942000 1.23701500 0.01009800 C 1.92220000 2.32949800 1.02957700 H 0.17357600 1.08390500 2.32432800 H 2.27674900 0.47621200 1.78397200 H 5.97213600 2.51620600 1.79495100 H 4.58342600 0.34385000 2.44977300 H 6.97517600 0.92120700 2.07890800 H 7.66390500 2.00776500 0.05247300 H 2.01713300 2.94383000 2.63086300 H 2.93276200 3.42774000 1.20162100 H 0.76962100 2.67820600 2.11495300 H 1.36856000 1.42894800 1.98244000 H 1.86003000 5.34755600 1.08013200 H 0.14537400 4.64909600 2.36153500 H 2.32579400 4.37694200 1.15953300 H 1.62164300 0.69559000 1.69995800 H 3.36233700 1.05121400 1.59013900 H 3.54688400 2.82033400 2.34848700 H 3.13217900 1.11091900 2.34136200 H 3.64194000 1.28051600 1.67286700 H 2.03199300 2.47288800 0.33018500 H 5.86847600 0.67370900 0.71604500 H 4.25139700 3.08164100 0.62190900 H 1.10498100 2.27679600 1.74908900 H 1.96318000 3.34725700 0.61980900 N 6.46431200 1.59255100 0.56829900 O 6.57444000 2.67431800 1.16386300 O 7.41044400 0.80360000 0.42713000 imaginary frequencies: 267 cm** 1 SCF Done: 1469.44686903 hartree zero point correction: 0.446526 hartree quasiharmonic free energy correction: 0.394601 hartree S62

exo TS2 g: O 1.18343600 3.33764300 0.15123300 N 2.51421700 1.47291900 0.53221200 C 0.10902000 1.25724400 0.49877900 H 0.09438700 0.30214200 0.99359300 C 4.03704000 0.40889100 0.79822000 C 2.68555500 0.15251800 0.73407400 H 1.93212400 0.35390900 1.32286400 C 1.21338700 2.12497000 0.43029300 C 6.34795600 0.32241500 0.10039200 H 7.14915000 0.16681500 0.44805600 C 4.29372900 1.57969800 1.52437500 H 3.49262700 2.05262100 2.08624100 C 5.06829100 0.22796600 0.08306800 C 5.57878600 2.12274100 1.53455800 H 5.78119900 3.02758700 2.10041100 C 3.68353800 2.29475400 0.13725100 H 3.29842500 3.13878400 0.43167500 C 6.60326400 1.49496200 0.82057100 H 7.60567400 1.91443200 0.82824500 N 1.86730700 0.78812800 0.93903600 C 0.04106200 2.31534000 0.27388200 H 0.30120200 3.37760800 0.20757700 C 0.90367400 1.60505000 1.28932600 S63

C 0.37981600 0.43046400 1.86740900 C 1.15306500 0.32080700 2.76318800 H 0.74123700 1.23146100 3.19108900 C 0.96099500 0.00809000 1.46595700 H 1.30600400 0.96817300 1.84376700 C 2.96627100 1.25699900 2.51634000 H 3.97473300 1.57842300 2.76240600 C 2.19702700 2.00658300 1.61943300 H 2.61074000 2.90459100 1.16637300 C 2.44247500 0.09501000 3.09170300 H 3.04222800 0.48926000 3.78407100 H 0.23368800 1.88427100 0.72004700 C 1.44473600 2.16115200 0.62890200 H 1.67432700 2.77116400 1.51437600 H 2.07724900 2.53986500 0.18030100 C 4.68859600 1.47666000 0.67032500 H 4.14858700 2.68384900 1.05115100 H 5.56685400 2.09439100 0.88284500 H 4.24069100 1.20050800 1.63572000 O 1.11496800 1.82759600 0.20550100 C 2.27399300 1.22692000 0.54672200 C 3.41068700 1.65231900 0.16821100 C 2.40124700 0.25237900 1.55651800 C 4.64742000 1.09378000 0.09248200 H 3.28741500 2.40369500 0.94031800 C 3.64326000 0.30559200 1.81911500 H 1.54637700 0.05389100 2.14654400 C 4.75915900 0.10636100 1.08305800 H 5.52406700 1.40137700 0.46394100 H 3.75656600 1.05357400 2.59430300 N 6.04796900 0.49177400 1.35072800 O 6.12094900 1.38207600 2.21036600 O 7.02981400 0.09052300 0.70944900 imaginary frequencies: 304 cm** 1 SCF Done: 1469.44424169 hartree zero point correction: 0.446654 hartree quasiharmonic free energy correction: 0.3880055 hartree S64

endo product (2,4) cis (4,5) cis 4gc: O 0.04226100 2.81109300 0.78882000 N 1.99379500 1.63306300 0.61748000 C 0.15686000 0.43800700 0.96217600 H 0.82050700 0.56514900 1.82141200 C 4.11059500 0.35798600 0.22780200 C 2.72225400 0.35385900 0.85607800 H 2.84906900 0.25328500 1.94409600 C 0.65283400 1.73850600 0.80405000 C 5.87847700 1.33124100 1.10038700 H 6.25614700 2.16046500 1.69450100 C 4.91331800 0.77191700 0.43865100 H 4.52265500 1.59279100 1.03363700 C 4.59498400 1.42460800 0.54294300 C 6.18490100 0.85576400 0.12277100 H 6.79551000 1.73868800 0.04589200 C 6.66885900 0.20137200 0.90073700 H 7.66112200 0.14793100 1.34091800 N 1.95658700 0.80102500 0.43389700 C 1.29482200 2.41079000 1.26349300 H 1.01394800 2.53024400 2.31669200 C 0.13405700 2.79431000 0.36891900 C 0.12436800 2.08144600 0.81192700 C 1.18531700 2.46427800 1.64160400 S65

H 1.37971400 1.90194600 2.55255600 C 0.68806800 0.84946000 1.16215800 H 0.93747900 0.87367100 2.23143400 C 1.74521400 4.26102200 0.13217100 H 2.37249900 5.10573400 0.14065300 C 0.68624900 3.88411700 0.69315200 H 0.49032000 4.43750700 1.60940900 C 1.99591800 3.54841600 1.30857900 H 2.81691100 3.83494100 1.96034900 H 2.12973000 3.10109300 1.07885800 C 1.78246400 0.98320600 1.01743900 H 1.08077500 0.25439200 1.44557300 H 2.74901200 0.83468900 1.50317300 C 3.74136300 2.65558400 0.74325400 H 3.14826300 2.56265600 1.66362600 O 0.94474700 0.29674600 0.23915200 C 2.27407300 0.56972600 0.23202500 C 3.05420700 0.19334000 1.11803500 C 2.86688900 1.56030700 0.56756400 C 4.42049900 0.01895500 1.19834800 H 2.57042100 0.95784800 1.71610100 C 4.23856500 1.76675400 0.49409400 H 2.24735600 2.18622200 1.19785600 C 5.00501800 0.99596300 0.38390100 H 5.03695000 0.56831200 1.86761600 H 4.71361200 2.52990300 1.09843800 H 4.37392300 3.54313400 0.85698700 C 2.79465000 2.84705900 0.43760900 H 2.10773500 3.67649300 0.27385200 H 3.36527500 3.04797500 1.35449900 N 6.44102600 1.21676000 0.45742700 O 6.94377600 2.06898500 0.28400800 O 7.09857200 0.54141400 1.25766500 SCF Done: 1469.53966911 hartree zero point correction: 0.451990 hartree quasiharmonic free energy correction: 0.401480 hartree S66

exo product (2,4) trans (4,5) trans 4gc: O 0.07170800 2.54194300 0.69710000 N 1.85684700 1.49759200 1.33357000 C 0.00976900 0.15343600 0.43699100 H 0.54516400 0.23616100 1.30967900 C 3.70524300 0.70226400 0.09139700 C 2.79973800 0.36911500 1.10343300 H 3.42566100 0.32046700 2.00147600 C 0.59693300 1.51480000 0.81357800 C 4.78052800 2.29793300 1.55489100 H 4.93582800 3.32868000 1.86685200 C 4.38376100 0.33065300 0.75072800 H 4.21370700 1.35385000 0.43036000 C 3.90561700 2.03780000 0.49061900 C 5.24708600 0.05666600 1.81039300 H 5.75882700 0.87004000 2.31798000 C 2.55089000 2.77602300 1.51394500 H 1.83777600 3.52036300 1.86913800 C 5.44708900 1.26623800 2.21418300 H 6.11997000 1.49348800 3.03701300 N 2.14339400 0.90569800 0.97605400 C 1.51212000 3.04221700 1.96789000 H 2.47462300 3.54010900 1.78639600 C 0.61803500 3.26659900 0.76619200 S67

C 0.44896500 2.26184700 0.20130100 C 0.31519100 2.52478800 1.34743500 H 0.42638800 1.74847800 2.09780400 C 1.05681100 0.88490300 0.00487300 H 1.46926400 0.53357200 0.95737500 C 0.77941900 4.75792500 0.55866200 H 1.25763900 5.72553700 0.68724000 C 0.00664800 4.50708200 0.57375900 H 0.12345300 5.28421900 1.32417400 C 0.93030200 3.76202400 1.52844100 H 1.52003300 3.94966800 2.42179700 H 1.07758800 3.51089400 2.85881600 C 1.77158200 1.56175700 2.23816900 H 2.60540600 1.45169300 2.93746800 H 0.89005000 1.10036200 2.71184000 C 3.18286300 3.19197400 0.18280100 H 3.31761100 2.62873600 2.28236800 H 3.87190300 4.03051400 0.33838200 H 2.38713800 3.55661100 0.48022400 O 0.91474600 0.32537100 0.65378300 C 2.23058700 0.56419700 0.44413300 C 2.78171100 0.99927500 0.77284600 C 3.06146800 0.34745100 1.55879100 C 4.15282400 1.19392800 0.87372500 H 2.14647400 1.22265900 1.61951800 C 4.42744400 0.54885500 1.46081000 H 2.61270600 0.01271900 2.48796800 C 4.96723800 0.96635400 0.23841100 H 4.59183000 1.53403200 1.80366200 H 5.07698800 0.37945100 2.31068600 N 6.40101600 1.17471700 0.12654400 O 7.10159000 0.98781900 1.12861500 O 6.86122200 1.52880400 0.96545500 SCF Done: 1469.54234975 hartree zero point correction: 0.452212 hartree quasiharmonic free energy correction: 0.401751 hartree S68