Stereodivergent, Diels–Alder-initiated organocascades employing α,β-unsaturated acylammonium salts: scope, mechanism, and application
Abbasov, Mikail E.; Hudson, Brandi M.; Tantillo, Dean J.; Romo, Daniel; Chem. Sci. 8 (2017) 1511–; doi:10.1039/C6SC04273B

data_1544356
_publ_section_title
;
 Stereodivergent, Diels--Alder-initiated organocascades employing
 \a,\b-unsaturated acylammonium salts: scope, mechanism, and application
;
_journal_issue                   2
_journal_name_full               'Chem. Sci.'
_journal_page_first              1511
_journal_paper_doi               10.1039/C6SC04273B
_journal_volume                  8
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H46 Br N O5 Si'
_chemical_formula_sum            'C33 H46 Br N O5 Si'
_chemical_formula_weight         644.71
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2013-10-02
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_audit_update_record
;
2013-11-15 deposited with the CCDC.
2016-10-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.0910(3)
_cell_length_b                   18.1061(7)
_cell_length_c                   20.6924(7)
_cell_measurement_reflns_used    9930
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      62.177
_cell_measurement_theta_min      3.244
_cell_volume                     3406.0(2)
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      110.15
_diffrn_measured_fraction_theta_full 0.869
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0645
_diffrn_reflns_av_unetI/netI     0.0421
_diffrn_reflns_Laue_measured_fraction_full 0.869
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            34574
_diffrn_reflns_point_group_measured_fraction_full 0.849
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         62.561
_diffrn_reflns_theta_min         3.243
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.285
_exptl_absorpt_correction_T_max  0.7522
_exptl_absorpt_correction_T_min  0.6042
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0836 before and 0.0653 after correction.
The Ratio of minimum to maximum transmission is 0.8032.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_description       column
_exptl_crystal_F_000             1360
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.319
_refine_diff_density_min         -0.512
_refine_diff_density_rms         0.065
_refine_ls_abs_structure_details
;
 Flack x determined using 1827 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.005(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.126
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     378
_refine_ls_number_reflns         5224
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.126
_refine_ls_R_factor_all          0.0423
_refine_ls_R_factor_gt           0.0328
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0308P)^2^+1.0419P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0707
_refine_ls_wR_factor_ref         0.0774
_reflns_Friedel_coverage         0.733
_reflns_Friedel_fraction_full    0.824
_reflns_Friedel_fraction_max     0.936
_reflns_number_gt                4621
_reflns_number_total             5224
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6sc04273b2.cif
_cod_data_source_block           1075c
_cod_depositor_comments          'Adding full bibliography for 1544356.cif.'
_cod_database_code               1544356
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.621
_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.a Ternary CH refined with riding coordinates:
 C1(H1A), C2(H2), C6(H6), C18(H18), C25(H25), C28(H28), C31(H31)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C8(H8A,H8B), C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C5(H5), C10(H10), C11(H11), C13(H13), C14(H14), C20(H20), C21(H21),
 C22(H22), C23(H23), C24(H24)
2.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C)
2.e Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_shelx_res_checksum              29786