Unique Steric Effect of Geminal Bis(silane) To Control the High Exo-selectivity in Intermolecular Diels-Alder Reaction.
Liu, Zengjin; Lin, Xinglong; Yang, Na; Su, Zhishan; Hu, Changwei; Xiao, Peihong; He, Yanyang; Song, Zhenlei; Journal of the American Chemical Society 138 (2016) 1877–1883; doi:10.1021/jacs.5b09689

data_4129702
_publ_section_title
;
 Unique Steric Effect of Geminal Bis(silane) To Control the High
 Exo-selectivity in Intermolecular Diels-Alder Reaction.
;
_journal_issue                   6
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1877
_journal_page_last               1883
_journal_paper_doi               10.1021/jacs.5b09689
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C35 H52 N2 O7 Si2'
_chemical_formula_sum            'C35 H52 N2 O7 Si2'
_chemical_formula_weight         668.96
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-01-31
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.660(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.5236(9)
_cell_length_b                   14.1625(6)
_cell_length_c                   17.3391(11)
_cell_measurement_reflns_used    3556
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.5910
_cell_measurement_theta_min      3.6120
_cell_volume                     3716.5(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -91.00  -56.50   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  178.0000 -120.0000 23

  2 omega  -94.00  -58.00   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  178.0000  150.0000 24

  3 omega  -20.00    5.50   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  -99.0000   30.0000 17

  4 omega -103.00  -77.50   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  178.0000   60.0000 17

  5 omega  -85.00  -58.00   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  -57.0000  150.0000 18

  6 omega  -43.00   98.00   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512    0.0000  -60.0000 94
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0030071000
_diffrn_orient_matrix_UB_12      0.0430856000
_diffrn_orient_matrix_UB_13      -0.0218309000
_diffrn_orient_matrix_UB_21      0.0439043000
_diffrn_orient_matrix_UB_22      -0.0061477000
_diffrn_orient_matrix_UB_23      0.0034205000
_diffrn_orient_matrix_UB_31      -0.0160841000
_diffrn_orient_matrix_UB_32      -0.0247845000
_diffrn_orient_matrix_UB_33      -0.0388274000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0502
_diffrn_reflns_av_unetI/netI     0.0680
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            16673
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         3.052
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.142
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33506
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.196
_exptl_crystal_description       needle
_exptl_crystal_F_000             1440
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.297
_refine_diff_density_min         -0.398
_refine_diff_density_rms         0.040
_refine_ls_extinction_coef       0.0060(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     489
_refine_ls_number_reflns         7323
_refine_ls_number_restraints     102
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.1158
_refine_ls_R_factor_gt           0.0677
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0584P)^2^+1.3300P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1512
_refine_ls_wR_factor_ref         0.1850
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4287
_reflns_number_total             7323
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b09689_si_003.cif
_cod_data_source_block           songzhl1018
_cod_database_code               4129702
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C1E) \\sim Ueq, Uanis(C26A) \\sim Ueq, Uanis(C1L) \\sim Ueq, Uanis(C27A)
\\sim Ueq, Uanis(C28A) \\sim Ueq, Uanis(C29A) \\sim Ueq, Uanis(C1H) \\sim Ueq,
Uanis(C1F) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C34A)
\\sim Ueq, Uanis(C34B) \\sim Ueq, Uanis(C35B) \\sim Ueq, Uanis(C35A) \\sim Ueq,
Uanis(C32B) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C32A) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
3. Others
 Fixed Sof: C1E(0.5) H1EA(0.5) H1EB(0.5) H1EC(0.5) C1F(0.5) H1FA(0.5)
 H1FB(0.5) C1H(0.5) H1HA(0.5) H1HB(0.5) H1HC(0.5) C1L(0.5) H1LA(0.5) H1LB(0.5)
 C26A(0.5) H26A(0.5) H26B(0.5) C27A(0.5) H27A(0.5) H27B(0.5) H27C(0.5)
 C28A(0.5) H28A(0.5) H28B(0.5) C29A(0.5) H29A(0.5) H29B(0.5) H29C(0.5)
 C32A(0.6) H32A(0.6) H32B(0.6) C32B(0.4) H32C(0.4) H32D(0.4) H33A(0.6)
 H33B(0.6) H33C(0.6) H33D(0.4) H33E(0.4) H33F(0.4) C34A(0.6) H34A(0.6)
 H34B(0.6) C34B(0.4) H34C(0.4) H34D(0.4) C35A(0.6) H35A(0.6) H35B(0.6)
 H35C(0.6) C35B(0.4) H35D(0.4) H35E(0.4) H35F(0.4)
4.a Ternary CH refined with riding coordinates:
 C6(H6), C8(H8), C23(H23)
4.b Secondary CH2 refined with riding coordinates:
 C1F(H1FA,H1FB), C1L(H1LA,H1LB), C2(H2A,H2B), C3(H3A,H3B), C15(H15A,H15B),
 C24(H24A,H24B), C26A(H26A,H26B), C28A(H28A,H28B), C30(H30A,H30B), C32A(H32A,
 H32B), C32B(H32C,H32D), C34A(H34A,H34B), C34B(H34C,H34D)
4.c Me refined with riding coordinates:
 C33(H33A,H33B,H33C), C33(H33D,H33E,H33F)
4.d Aromatic/amide H refined with riding coordinates:
 C5(H5A), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C18(H18), C20(H20),
  C22(H22)
4.e Idealised Me refined as rotating group:
 C1E(H1EA,H1EB,H1EC), C1H(H1HA,H1HB,H1HC), C7(H7A,H7B,H7C), C25(H25A,H25B,
 H25C), C27A(H27A,H27B,H27C), C29A(H29A,H29B,H29C), C31(H31A,H31B,H31C),
 C35A(H35A,H35B,H35C), C35B(H35D,H35E,H35F)
4.f Idealised tetrahedral OH refined as rotating group:
 O5(H5)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'