SUPPORTING INFORMATION. Diastereoselective synthesis of nitroso acetals from (S,E)- -aminated

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1 SUPPORTING INFORMATION for Diastereoselective synthesis of nitroso acetals from (S,E)- -aminated nitroalkenes via multicomponent [4 + 2]/[3 + 2] cycloadditions promoted by LiCl or LiClO 4 Leandro Lara de Carvalho 1, Robert Alan Burrow 2 and Vera Lúcia Patrocinio Pereira* 1, Address: 1 Núcleo de Pesquisas de Produtos Naturais, Laboratório de Síntese Estereosseletiva de Substâncias Bioativas, Universidade Federal do Rio de Janeiro, , Rio de Janeiro, Brazil and 2 Departamento de Química, Laboratório de Materiais Inorgânicos, Universidade Federal de Santa Maria, , Santa Maria, Rio Grande do Sul, RS, Brazil Vera Lúcia Patrocinio Pereira - patrocinio@correio.nppn.ufrj.br Corresponding author Tel.: ; Fax: Dataset of X-ray crystallography and extended ORTEP drawing of 11b S1

2 X-RAY DIFFRACTION EXPERIMENTS OF 11b The Cambridge Crystallographic Data Centre (CCDC) register number CN Bn 2 N a H Bn O N O 6 OEt A colorless Block-like specimen of C 31 H 35 N 3 O 3, approximate dimensions mm mm mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. S2

3 Table 1: Data collection details for 11b. Axis dx/ mm 2θ/ ω/ φ/ χ/ Width/ Frames Time/ s Wave length/ Å Voltage/ kv Current/ ma Omega Omega Omega Omega Omega Omega Omega Omega Omega Omega Omega Omega Omega Omega Omega Phi Omega Omega Omega Omega Omega Omega Omega Omega Omega Omega Omega Omega Omega A total of 2829 frames were collected. The total exposure time was 7.86 hours. The frames were integrated with the Bruker SAINT software package using a narrow-frame algorithm. The integration of the data using a monoclinic unit cell yielded a total of 6961 reflections to a maximum θ angle of (0.75 Å resolution), of which 6961 were independent (average redundancy 1.000, completeness = 99.4%, Rsig = 5.40%) and 3665 (52.65%) were greater than 2σ(F2). The final cell constants of a = (5) Å, b = (6) Å, c = (6) Å, β = (2), volume = (12) Å 3, are based upon the refinement of the XYZ-centroids of 9906 reflections above 20 σ(i) with < 2θ < The calculated minimum and maximum transmission coefficients (based on crystal size) are and The crystal was twinned with two main components in a 3:1 intensity ratio. The integration was performed considering both components. During the scaling, only reflections belonging to the more intense component were output for solution and refinement. The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group P , with Z = 2 for the formula unit, C31H35N3O3. The final anisotropic full-matrix least-squares refinement on F2 with 336 variables converged at R1 = 5.01%, for the observed data and wr2 = 11.61% for all data. The goodness-of-fit was The largest peak in the final difference electron density synthesis was e-/å3 and the largest hole was e-/å 3 with an RMS deviation of e-/å 3. On the basis of the final model, the calculated density was g/cm 3 and F(000), 532 e-. S3

4 CN 4 Bn 2 N 3 2 3a H Bn O N O 6 OEt S4

5 Table 2: Sample and crystal data for 11b. Identification code RB_UFRJ_LL271a Chemical formula C31H35N3O3 Formula weight Temperature 296(2) K Wavelength Å Crystal size x x mm Crystal habit colorless Block Crystal system monoclinic Space group P Unit cell dimensions a = (5) Å α = 90 b = (6) Å β = (2) c = (6) Å γ = 90 Volume (12) Å3 Z 2 Density (calculated) Mg/cm3 Absorption coefficient mm-1 F(000) 532 Table 3: Data collection and structure refinement for 11b. Theta range for data collection 2.06 to Index ranges -13<=h<=13, -14<=k<=15, -16<=l<=16 Reflections collected 6961 Coverage of independent reflections 99.4% Max. and min. transmission and Structure solution technique direct methods Structure solution program SHELXS-97 (Sheldrick, 2008) Refinement method Full-matrix least-squares on F2 Refinement program SHELXL-97 (Sheldrick, 2008) Function minimized Σ w(fo2 - Fc2)2 Data / restraints / parameters 6961 / 1 / 336 Goodness-of-fit on F Final R indices 3665 data; I>2σ(I) R1 = , wr2 = all data R1 = , wr2 = Weighting scheme w=1/[σ2(fo2)+(0.0544p) p] where P=(Fo2+2Fc2)/3 Absolute structure parameter 0.0(11) Extinction coefficient (19) Largest diff. peak and hole and eå-3 R.M.S. deviation from mean eå-3 S5

6 Table 4: Atomic coordinates and equivalent isotropic atomic displacement parameters (Å2) for 11b. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x/a y/b z/c U(eq) O (13) (18) (14) (5) C (2) (2) (2) (7) C (19) (2) (19) (6) C3A (17) (19) (17) (5) C (16) (19) (16) (5) C (2) (2) (17) (6) C (2) (2) (19) (6) C (3) (3) (2) (8) O (14) (14) (12) (4) C (4) (4) (3) (13) N (15) (17) (14) (5) O (14) (15) (13) (4) C (2) (3) (3) (9) N (3) (4) (3) (16) C (18) (2) (2) (6) N (15) (15) (14) (4) C (18) (19) (17) (5) C (2) (2) (18) (6) C (2) (2) (19) (6) C (18) (2) (19) (6) C (3) (3) (2) (9) C (4) (4) (5) (14) C (4) (3) (5) (15) C (3) (4) (4) (12) C (2) (3) (2) (8) C (2) (19) (19) (6) C (3) (2) (2) (8) C (5) (3) (2) (11) C (4) (4) (3) (11) C (3) (4) (3) (10) C (2) (3) (2) (7) C (19) (2) (16) (5) C (2) (2) (19) (6) C (2) (3) (19) (7) C (3) (2) (2) (7) C (3) (2) (2) (7) C (2) (2) (18) (6) Table 5: Bond lengths (Å) for 11b. O1-N (2) O1-C (3) C2-C (4) C2-C (3) C2-H C3-C3A 1.518(3) C3-H3A 0.97 C3-H3B 0.97 C3A-N (3) C3A-C (2) S6

7 C3A-H3AA 0.98 C4-C (3) C4-C (3) C4-H C5-C (3) C5-H5A 0.97 C5-H5B 0.97 C6-O (3) C6-O (2) C6-H C7-O (3) C7-C (4) C7-H7A 0.97 C7-H7B 0.97 O7-N (2) C8-H8A 0.96 C8-H8B 0.96 C8-H8C 0.96 C9-N (4) C10-C (3) C10-C (3) C10-H10A 0.97 C10-H10B 0.97 N10-C (3) N10-C (3) N10-C (3) C11-H C12-C (3) C12-H12A 0.97 C12-H12B 0.97 C13-C (3) C13-H13A 0.97 C13-H13B 0.97 C14-C (3) C14-C (3) C15-C (6) C15-H C16-C (6) C16-H C17-C (6) C17-H C18-C (5) C18-H C19-H C20-C (3) C20-C (3) C21-C (4) C21-H C22-C (5) C22-H C23-C (5) C23-H C24-C (4) C24-H C25-H C26-C (3) C26-C (3) C27-C (3) C27-H C28-C (4) C28-H C29-C (4) C29-H C30-C (3) C30-H C31-H Table 6: Bond angles ( ) for 11b. N8-O1-C (15) O1-C2-C (2) O1-C2-C (16) C9-C2-C (2) O1-C2-H C9-C2-H C3-C2-H C2-C3-C3A (18) C2-C3-H3A C3A-C3-H3A C2-C3-H3B C3A-C3-H3B H3A-C3-H3B N8-C3A-C (16) N8-C3A-C (16) C3-C3A-C (17) N8-C3A-H3AA C3-C3A-H3AA C4-C3A-H3AA C5-C4-C (16) C5-C4-C3A (16) C11-C4-C3A (16) C5-C4-H C11-C4-H S7

8 C3A-C4-H C6-C5-C (17) C6-C5-H5A C4-C5-H5A C6-C5-H5B C4-C5-H5B H5A-C5-H5B O8-C6-O (17) O8-C6-C (18) O7-C6-C (17) O8-C6-H O7-C6-H C5-C6-H O8-C7-C (3) O8-C7-H7A C8-C7-H7A O8-C7-H7B C8-C7-H7B H7A-C7-H7B C6-O7-N (15) C7-C8-H8A C7-C8-H8B H8A-C8-H8B C7-C8-H8C H8A-C8-H8C H8B-C8-H8C O1-N8-O (15) O1-N8-C3A (14) O7-N8-C3A (15) C6-O8-C (19) N9-C9-C (3) C14-C10-C (16) C14-C10-H10A C11-C10-H10A C14-C10-H10B C11-C10-H10B H10A-C10-H10B C11-N10-C (15) C11-N10-C (17) C13-N10-C (17) N10-C11-C (17) N10-C11-C (16) C4-C11-C (17) N10-C11-H C4-C11-H C10-C11-H N10-C12-C (18) N10-C12-H12A C20-C12-H12A N10-C12-H12B C20-C12-H12B H12A-C12-H12B N10-C13-C (15) N10-C13-H13A C26-C13-H13A N10-C13-H13B C26-C13-H13B H13A-C13-H13B C15-C14-C (3) C15-C14-C (2) C19-C14-C (2) C14-C15-C (3) C14-C15-H C16-C15-H C17-C16-C (4) C17-C16-H C15-C16-H C16-C17-C (4) C16-C17-H C18-C17-H C17-C18-C (4) C17-C18-H C19-C18-H C18-C19-C (3) C18-C19-H C14-C19-H C21-C20-C (2) C21-C20-C (2) C25-C20-C (2) C20-C21-C (3) C20-C21-H C22-C21-H C23-C22-C (3) C23-C22-H C21-C22-H C24-C23-C (3) C24-C23-H C22-C23-H C23-C24-C (3) C23-C24-H C25-C24-H C24-C25-C (3) C24-C25-H C20-C25-H C31-C26-C (2) C31-C26-C (19) S8

9 C27-C26-C (2) C28-C27-C (2) C28-C27-H C26-C27-H C29-C28-C (2) C29-C28-H C27-C28-H C30-C29-C (2) C30-C29-H C28-C29-H C29-C30-C (2) C29-C30-H C31-C30-H C26-C31-C (2) C26-C31-H C30-C31-H Table 7: Torsion angles ( ) for 11b. N8-O1-C2-C (19) N8-O1-C2-C3-8.2(3) O1-C2-C3-C3A -12.1(3) C9-C2-C3-C3A 104.9(3) C2-C3-C3A-N8 27.2(2) C2-C3-C3A-C (19) N8-C3A-C4-C5-17.9(2) C3-C3A-C4-C (2) N8-C3A-C4-C (17) C3-C3A-C4-C (2) C11-C4-C5-C (17) C3A-C4-C5-C6 63.5(2) C4-C5-C6-O (17) C4-C5-C6-O7-36.2(2) O8-C6-O7-N (19) C5-C6-O7-N8-33.6(2) C2-O1-N8-O7-82.7(2) C2-O1-N8-C3A 25.7(2) C6-O7-N8-O (15) C6-O7-N8-C3A 81.11(17) C3-C3A-N8-O1-32.9(2) C4-C3A-N8-O (17) C3-C3A-N8-O (17) C4-C3A-N8-O (18) O7-C6-O8-C7 68.1(2) C5-C6-O8-C (17) C8-C7-O8-C (2) O1-C2-C9-N9 138.(9) C3-C2-C9-N9 21.(10) C13-N10-C11-C4 86.7(2) C12-N10-C11-C (16) C13-N10-C11-C (3) C12-N10-C11-C (2) C5-C4-C11-N (2) C3A-C4-C11-N (2) C5-C4-C11-C (2) C3A-C4-C11-C (17) C14-C10-C11-N (19) C14-C10-C11-C4 57.4(2) C11-N10-C12-C (2) C13-N10-C12-C (19) C11-N10-C13-C (18) C12-N10-C13-C (2) C11-C10-C14-C (2) C11-C10-C14-C (3) C19-C14-C15-C16-0.5(4) C10-C14-C15-C (2) C14-C15-C16-C17 0.0(5) C15-C16-C17-C18 0.8(5) C16-C17-C18-C19-1.1(5) C17-C18-C19-C14 0.6(5) C15-C14-C19-C18 0.2(4) C10-C14-C19-C (2) N10-C12-C20-C (2) N10-C12-C20-C (3) C25-C20-C21-C22-1.8(4) C12-C20-C21-C (2) C20-C21-C22-C23 1.2(4) C21-C22-C23-C24 0.3(5) C22-C23-C24-C25-1.1(5) C23-C24-C25-C20 0.6(4) C21-C20-C25-C24 0.9(4) C12-C20-C25-C (3) N10-C13-C26-C (2) N10-C13-C26-C (3) C31-C26-C27-C28-1.5(3) C13-C26-C27-C (2) C26-C27-C28-C29 1.4(3) C27-C28-C29-C30-1.0(4) C28-C29-C30-C31 0.7(4) C27-C26-C31-C30 1.3(3) C13-C26-C31-C (2) C29-C30-C31-C26-0.9(3) S9

10 Table 8: Anisotropic atomic displacement parameters (Å2) for 11b. The anisotropic atomic displacement factor exponent takes the form: -2π2[ h2 a*2 U h k a* b* U12 ] U11 U22 U33 U23 U13 U12 O (8) (15) (11) (11) (7) (9) C (12) (17) (16) (13) (11) (12) C (11) (16) (14) (13) (10) (11) C3A (10) (13) (13) (10) (9) (9) C (9) (13) (12) (10) (8) (10) C (10) (15) (13) (12) (9) (11) C (12) (17) (15) (11) (10) (11) C (15) (19) (19) (16) (13) (14) O (9) (10) (10) (8) (7) (8) C (4) 0.144(3) 0.082(2) 0.027(2) 0.062(2) 0.003(3) N (9) (13) (11) (10) (8) (9) O (10) (10) (10) (8) (7) (8) C (13) 0.137(3) 0.100(2) 0.044(2) (13) (16) N (15) 0.241(4) 0.157(3) 0.104(3) (16) (19) C (11) (16) (16) (11) (10) (10) N (9) (12) (11) (9) (8) (8) C (10) (14) (13) (10) (9) (9) C (13) (14) (14) (12) (11) (11) C (11) (15) (15) (12) (10) (11) C (10) (17) (16) (13) (10) (10) C (16) 0.105(3) 0.094(2) (18) (15) (17) C (3) 0.113(3) 0.165(4) 0.075(3) 0.086(3) 0.045(3) C (3) 0.078(2) 0.227(5) 0.005(3) 0.109(3) 0.000(2) C (18) 0.109(3) 0.167(4) (3) 0.047(2) (19) C (13) 0.088(2) 0.105(2) (17) (13) (13) C (13) (15) (14) (11) (11) (11) C (19) (19) (16) (15) (15) (15) C (3) 0.080(2) (19) (16) (2) 0.003(2) C (3) 0.106(3) 0.090(3) 0.017(2) (19) (2) C (16) 0.144(3) 0.079(2) 0.032(2) (15) (17) C (14) (19) (16) (13) (12) (13) C (11) (14) (13) (10) (9) (11) C (14) (16) (16) (13) (12) (13) C (14) 0.084(2) (17) (14) (12) (15) C (17) (19) (18) (14) (14) (14) C (17) (17) (19) (14) (14) (14) C (12) (16) (14) (12) (10) (13) S10

11 Table 9: Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å2) for 11b. x/a y/b z/c U(eq) H H3A H3B H3AA H H5A H5B H H7A H7B H8A H8B H8C H10A H10B H H12A H12B H13A H13B H H H H H H H H H H H H H H H S11