Divergent synthesis of polysubstituted cyclopropanes and β-silyoxy imidates via switchable additions of N-tert-butanesulfinylimidates to acylsilanes
Tang, Fan; Ma, Peng-Ju; Yao, Yun; Xu, Yan-Jun; Lu, Chong-Dao; Chemical Communications  (2019) –; doi:10.1039/C9CC00963A

data_7123144
_publ_section_title
;
 Divergent synthesis of polysubstituted cyclopropanes and \b-silyoxy
 imidates via switchable additions of N-tert-butanesulfinylimidates to
 acylsilanes
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC00963A
_journal_year                    2019
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C21 H37 N O3 S Si, H2 O'
_chemical_formula_sum            'C21 H39 N O4 S Si'
_chemical_formula_weight         429.68
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-23
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-01-21 deposited with the CCDC.    2019-03-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.113(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.2420(5)
_cell_length_b                   6.4724(3)
_cell_length_c                   14.3242(5)
_cell_measurement_reflns_used    5986
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.6860
_cell_measurement_theta_min      3.0160
_cell_volume                     1226.86(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     71.00  97.00   1.00    1.00    --   40.73-125.00-180.00   26
  2  \w     50.00  95.00   1.00    1.00    --  107.58 -95.00 -60.00   45
  3  \w     36.00 103.00   1.00    1.00    --  107.58 -61.00-180.00   67
  4  \w     74.00 174.00   1.00    1.00    --  107.58  15.00-120.00  100
  5  \w     87.00 175.00   1.00    1.00    --  107.58  45.00 120.00   88
  6  \w     34.00 131.00   1.00    1.00    --  107.58 -30.00-150.00   97
  7  \w    -82.00 -57.00   1.00    1.00    --  -40.73-150.00 -11.00   25
  8  \w   -115.00 -20.00   1.00    1.00    --  -40.73 -38.00 -90.00   95
  9  \w   -109.00 -20.00   1.00    1.00    --  -40.73 -38.00   0.00   89
 10  \w    -35.00 -10.00   1.00    1.00    --  -41.23 125.00 150.00   25
 11  \w    -70.00 -44.00   1.00    1.00    --  -41.23 -77.00-150.00   26
 12  \w    -61.00  29.00   1.00    1.00    --  -41.23  38.00 -30.00   90
 13  \w     10.00  67.00   1.00    1.00    --   41.23  77.00-120.00   57
 14  \w     17.00  54.00   1.00    1.00    --   41.23  38.00 -30.00   37
 15  \w     75.00 101.00   1.00    1.00    --  107.58  77.00-150.00   26
 16  \w     80.00 106.00   1.00    1.00    --  107.58  61.00 -90.00   26
 17  \w    150.00 176.00   1.00    1.00    --  107.58  45.00 -30.00   26
 18  \w     78.00 104.00   1.00    1.00    --  107.58  61.00-180.00   26
 19  \w     78.00 104.00   1.00    1.00    --  107.58  61.00 -60.00   26
 20  \w     85.00 111.00   1.00    1.00    --  107.58  45.00 -90.00   26
 21  \w     75.00 100.00   1.00    1.00    --  107.58  77.00-120.00   25
 22  \w    108.00 133.00   1.00    1.00    --  107.58 -45.00 -30.00   25
 23  \w     75.00 101.00   1.00    1.00    --  107.58  77.00 -60.00   26
 24  \w     82.00 108.00   1.00    1.00    --  107.58  45.00 -60.00   26
 25  \w     79.00 104.00   1.00    1.00    --  107.58  61.00-150.00   25
 26  \w     75.00 101.00   1.00    1.00    --  107.58  77.00 -90.00   26
 27  \w     76.00 102.00   1.00    1.00    --  107.58  77.00-180.00   26
 28  \w     80.00 106.00   1.00    1.00    --  107.58  61.00 -30.00   26
 29  \w     82.00 108.00   1.00    1.00    --  107.58  45.00-150.00   26
 30  \w     78.00 104.00   1.00    1.00    --  107.58  61.00-120.00   26
 31  \w     86.00 112.00   1.00    1.00    --  107.58  45.00-120.00   26
 32  \w     35.00 104.00   1.00    1.00    --  107.58 -45.00 -30.00   69
 33  \w     83.00 108.00   1.00    1.00    --  107.58  30.00-150.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0196543000
_diffrn_orient_matrix_UB_12      -0.0092513000
_diffrn_orient_matrix_UB_13      -0.1052701000
_diffrn_orient_matrix_UB_21      -0.1110617000
_diffrn_orient_matrix_UB_22      -0.0614092000
_diffrn_orient_matrix_UB_23      -0.0203366000
_diffrn_orient_matrix_UB_31      -0.0287752000
_diffrn_orient_matrix_UB_32      0.2297651000
_diffrn_orient_matrix_UB_33      -0.0095977000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0439
_diffrn_reflns_av_unetI/netI     0.0498
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            9985
_diffrn_reflns_point_group_measured_fraction_full 0.952
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.924
_diffrn_reflns_theta_min         3.087
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.833
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56533
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.163
_exptl_crystal_description       block
_exptl_crystal_F_000             468
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.963
_refine_diff_density_min         -0.486
_refine_diff_density_rms         0.092
_refine_ls_abs_structure_details
;
 Flack x determined using 1793 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.027(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         4600
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0634
_refine_ls_R_factor_gt           0.0625
_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^)+(0.0583P)^2^+5.0391P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1695
_refine_ls_wR_factor_ref         0.1701
_reflns_Friedel_coverage         0.727
_reflns_Friedel_fraction_full    0.895
_reflns_Friedel_fraction_max     0.862
_reflns_number_gt                4516
_reflns_number_total             4600
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc00963a2.cif
_cod_data_source_block           4a
_cod_database_code               7123144
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2.a Riding coordinates:
 N1(H1)
2.b Free rotating group:
 O1W(H1WA,H1WB)
2.c Ternary CH refined with riding coordinates:
 C2(H2)
2.d Aromatic/amide H refined with riding coordinates:
 C10(H10), C6(H6), C9(H9), C7(H7), C8(H8)
2.e Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C4(H4A,H4B,
 H4C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C19(H19A,H19B,H19C), C15(H15A,
 H15B,H15C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.501
_oxdiff_exptl_absorpt_empirical_full_min 0.680