Acylammonium salts as dienophiles in diels-alder/lactonization organocascades.
Abbasov, Mikail E.; Hudson, Brandi M.; Tantillo, Dean J.; Romo, Daniel; Journal of the American Chemical Society 136 (2014) 4492–4495; doi:10.1021/ja501005g

data_4121519
_publ_section_title
;
 Acylammonium salts as dienophiles in diels-alder/lactonization
 organocascades.
;
_journal_issue                   12
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4492
_journal_page_last               4495
_journal_paper_doi               10.1021/ja501005g
_journal_volume                  136
_journal_year                    2014
_chemical_absolute_configuration abs
_chemical_formula_moiety         'C30 H46 Br N O5 Si'
_chemical_formula_sum            'C30 H46 Br N O5 Si'
_chemical_formula_weight         608.68
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2013-09-27
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                89.539(5)
_cell_angle_beta                 89.620(5)
_cell_angle_gamma                87.393(5)
_cell_formula_units_Z            4
_cell_length_a                   13.4034(9)
_cell_length_b                   13.4037(9)
_cell_length_c                   17.8225(13)
_cell_measurement_reflns_used    9849
_cell_measurement_temperature    110
_cell_measurement_theta_max      57.96
_cell_measurement_theta_min      2.48
_cell_volume                     3198.4(4)
_computing_cell_refinement       'Bruker FRAMBO'
_computing_data_collection       'Bruker FRAMBO'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      110
_diffrn_detector                 'MWPC area detector'
_diffrn_detector_type            'Bruker Hi_Star area detector'
_diffrn_measured_fraction_theta_full 0.896
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'MWPC area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_collimation    0.5mm
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0831
_diffrn_reflns_av_unetI/netI     0.1425
_diffrn_reflns_Laue_measured_fraction_full 0.896
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            55755
_diffrn_reflns_point_group_measured_fraction_full 0.889
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         64.370
_diffrn_reflns_theta_min         2.479
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_target            Cu
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.400
_exptl_absorpt_correction_T_max  0.7524
_exptl_absorpt_correction_T_min  0.6304
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1218 before and 0.0863 after correction.
The Ratio of minimum to maximum transmission is 0.8379.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.264
_exptl_crystal_F_000             1288
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.840
_refine_diff_density_min         -0.735
_refine_diff_density_rms         0.099
_refine_ls_abs_structure_details
;
 Flack x determined using 5668 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.030(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1372
_refine_ls_number_reflns         18937
_refine_ls_number_restraints     2631
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.1063
_refine_ls_R_factor_gt           0.0896
_refine_ls_shift/su_max          0.012
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+10.2589P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2171
_refine_ls_wR_factor_ref         0.2373
_reflns_Friedel_coverage         0.986
_reflns_Friedel_fraction_full    0.883
_reflns_Friedel_fraction_max     0.953
_reflns_number_gt                15936
_reflns_number_total             18937
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja501005g_si_004.cif
_cod_data_source_block           dr89
_cod_database_code               4121519
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.778
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Br1_1 \\sim Si1_1 \\sim O1_1 \\sim O2_1 \\sim O3_1 \\sim O4_1 \\sim O5_1 \\sim
N1_1 \\sim C1_1 \\sim C2_1 \\sim C3_1 \\sim C4_1 \\sim C5_1 \\sim C6_1 \\sim
C7_1 \\sim C8_1 \\sim C9_1 \\sim C10_1 \\sim C11_1 \\sim C12_1 \\sim C13_1
\\sim C14_1 \\sim C15_1 \\sim C16_1 \\sim C17_1 \\sim C18_1 \\sim C19_1 \\sim
C20_1 \\sim C21_1 \\sim C22_1 \\sim C23_1 \\sim C24_1 \\sim C25_1 \\sim C26_1
\\sim C27_1 \\sim C28_1 \\sim C29_1 \\sim C30_1 \\sim Br1_2 \\sim Si1_2 \\sim
O1_2 \\sim O2_2 \\sim O3_2 \\sim O4_2 \\sim O5_2 \\sim N1_2 \\sim C1_2 \\sim
C2_2 \\sim C3_2 \\sim C4_2 \\sim C5_2 \\sim C6_2 \\sim C7_2 \\sim C8_2 \\sim
C9_2 \\sim C10_2 \\sim C11_2 \\sim C12_2 \\sim C13_2 \\sim C14_2 \\sim C15_2
\\sim C16_2 \\sim C17_2 \\sim C18_2 \\sim C19_2 \\sim C20_2 \\sim C21_2 \\sim
C22_2 \\sim C23_2 \\sim C24_2 \\sim C25_2 \\sim C26_2 \\sim C27_2 \\sim C28_2
\\sim C29_2 \\sim C30_2 \\sim Br1_3 \\sim Si1_3 \\sim O1_3 \\sim O2_3 \\sim
O3_3 \\sim O4_3 \\sim O5_3 \\sim N1_3 \\sim C1_3 \\sim C2_3 \\sim C3_3 \\sim
C4_3 \\sim C5_3 \\sim C6_3 \\sim C7_3 \\sim C8_3 \\sim C9_3 \\sim C10_3 \\sim
C11_3 \\sim C12_3 \\sim C13_3 \\sim C14_3 \\sim C15_3 \\sim C16_3 \\sim C17_3
\\sim C18_3 \\sim C19_3 \\sim C20_3 \\sim C21_3 \\sim C22_3 \\sim C23_3 \\sim
C24_3 \\sim C25_3 \\sim C26_3 \\sim C27_3 \\sim C28_3 \\sim C29_3 \\sim C30_3
\\sim Br1_4 \\sim Si1_4 \\sim O1_4 \\sim O2_4 \\sim O3_4 \\sim O4_4 \\sim O5_4
\\sim N1_4 \\sim C1_4 \\sim C2_4 \\sim C3_4 \\sim C4_4 \\sim C5_4 \\sim C6_4
\\sim C7_4 \\sim C8_4 \\sim C9_4 \\sim C10_4 \\sim C11_4 \\sim C12_4 \\sim
C13_4 \\sim C14_4 \\sim C15_4 \\sim C16_4 \\sim C17_4 \\sim C18_4 \\sim C19_4
\\sim C20_4 \\sim C21_4 \\sim C22_4 \\sim C23_4 \\sim C24_4 \\sim C25_4 \\sim
C26_4 \\sim C27_4 \\sim C28_4 \\sim C29_4 \\sim C30_4: within 1.7A with sigma
of 0.005 and sigma for terminal atoms of 0.005
3. Rigid body (RIGU) restrains
 Br1_1, Si1_1, O1_1, O2_1, O3_1, O4_1, O5_1, N1_1, C1_1, C2_1, C3_1, C4_1,
 C5_1, C6_1, C7_1, C8_1, C9_1, C10_1, C11_1, C12_1, C13_1, C14_1, C15_1, C16_1,
 C17_1, C18_1, C19_1, C20_1, C21_1, C22_1, C23_1, C24_1, C25_1, C26_1, C27_1,
 C28_1, C29_1, C30_1
 Br1_2, Si1_2, O1_2, O2_2, O3_2, O4_2, O5_2, N1_2, C1_2, C2_2, C3_2, C4_2,
 C5_2, C6_2, C7_2, C8_2, C9_2, C10_2, C11_2, C12_2, C13_2, C14_2, C15_2, C16_2,
 C17_2, C18_2, C19_2, C20_2, C21_2, C22_2, C23_2, C24_2, C25_2, C26_2, C27_2,
 C28_2, C29_2, C30_2
 Br1_3, Si1_3, O1_3, O2_3, O3_3, O4_3, O5_3, N1_3, C1_3, C2_3, C3_3, C4_3,
 C5_3, C6_3, C7_3, C8_3, C9_3, C10_3, C11_3, C12_3, C13_3, C14_3, C15_3, C16_3,
 C17_3, C18_3, C19_3, C20_3, C21_3, C22_3, C23_3, C24_3, C25_3, C26_3, C27_3,
 C28_3, C29_3, C30_3
 Br1_4, Si1_4, O1_4, O2_4, O3_4, O4_4, O5_4, N1_4, C1_4, C2_4, C3_4, C4_4,
 C5_4, C6_4, C7_4, C8_4, C9_4, C10_4, C11_4, C12_4, C13_4, C14_4, C15_4, C16_4,
 C17_4, C18_4, C19_4, C20_4, C21_4, C22_4, C23_4, C24_4, C25_4, C26_4, C27_4,
 C28_4, C29_4, C30_4
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4.a Riding coordinates:
 O5(H5), O5(H5)
4.b Ternary CH refined with riding coordinates:
 C3(H3), C4(H4), C5(H5A), C6(H6), C11(H11), C14(H14), C17(H17), C3(H3), C4(H4),
  C5(H5A), C6(H6), C11(H11), C14(H14), C17(H17), C3(H3), C4(H4), C5(H5A),
 C6(H6), C11(H11), C14(H14), C17(H17), C3(H3), C4(H4), C5(H5A), C6(H6),
 C11(H11), C14(H14), C17(H17)
4.c Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C21(H21A,H21B), C24(H24A,
 H24B), C2(H2A,H2B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C21(H21A,H21B),
 C24(H24A,H24B), C2(H2A,H2B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C21(H21A,
 H21B), C24(H24A,H24B), C2(H2A,H2B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B),
 C21(H21A,H21B), C24(H24A,H24B)
4.d Me refined with riding coordinates:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C22(H22A,H22B,H22C), C12(H12A,
 H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C22(H22A,H22B,H22C), C12(H12A,H12B,
 H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,
 H18B,H18C), C19(H19A,H19B,H19C), C22(H22A,H22B,H22C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C22(H22A,H22B,H22C)
4.e Aromatic/amide H refined with riding coordinates:
 N1(H1), C26(H26), C27(H27), C29(H29), C30(H30), N1(H1), C26(H26), C27(H27),
 C29(H29), C30(H30), N1(H1), C26(H26), C27(H27), C29(H29), C30(H30), N1(H1),
 C26(H26), C27(H27), C29(H29), C30(H30)
4.f Idealised tetrahedral OH refined as rotating group:
 O5(H5), O5(H5)
;
_shelx_res_checksum              62065
_shelx_hkl_checksum              17428