Highly enantioselective synthesis of spirocyclopropyloxindoles via a Rh(ii)-catalyzed asymmetric cyclopropanation reaction.
Chi, Yongjian; Qiu, Lihua; Xu, Xinfang; Organic & biomolecular chemistry 14 (2016) 10357–10361; doi:10.1039/c6ob02160c

data_7155322
_publ_section_title
;
 Highly enantioselective synthesis of spirocyclopropyloxindoles via a
 Rh(ii)-catalyzed asymmetric cyclopropanation reaction.
;
_journal_issue                   44
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              10357
_journal_page_last               10361
_journal_paper_doi               10.1039/c6ob02160c
_journal_volume                  14
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H20 Cl N O3'
_chemical_formula_sum            'C21 H20 Cl N O3'
_chemical_formula_weight         369.83
_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
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-01-04
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2016-01-18 deposited with the CCDC.
2016-10-18 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   11.3609(3)
_cell_length_b                   11.3606(3)
_cell_length_c                   14.5605(4)
_cell_measurement_reflns_used    9852
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      73.3840
_cell_measurement_theta_min      3.0210
_cell_volume                     1879.27(9)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 10.4471
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
  1 omega -109.00  -10.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.9843  -57.0000 -150.0000 99

  2 omega  -70.00   36.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.9843   77.0000   30.0000 106

  3 omega  -45.00   36.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.9843   37.0000    0.0000 81

  4 omega  -41.00   28.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.9843   37.0000  150.0000 69

  5 omega   44.00   82.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       39.9843 -125.0000 -180.0000 38

  6 omega   59.00   99.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -45.0000 -120.0000 40

  7 omega   51.00   95.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -45.0000  -30.0000 44

  8 omega   25.00   84.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -94.0000 -150.0000 59

  9 omega   47.00  109.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -94.0000  -90.0000 62

 10 omega   44.00   90.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -30.0000   60.0000 46

 11 omega   52.00  116.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522 -111.0000 -180.0000 64

 12 omega   75.00  174.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   30.0000  -30.0000 99

 13 omega   47.00  106.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -94.0000    0.0000 59

 14 omega   77.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   30.0000   30.0000 101

 15 omega   22.00   94.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -94.0000   90.0000 72

 16 omega  121.00  171.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   61.0000 -120.0000 50

 17 omega   59.00   87.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -30.0000 -180.0000 28

 18 omega   76.00  108.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   61.0000 -120.0000 32

 19 omega -114.00  -10.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.9843  -57.0000  -60.0000 104

 20 omega -119.00   -6.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.9843  -77.0000   30.0000 113

 21 omega -116.00  -14.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.9843  -37.0000   90.0000 102

 22 omega   -4.00   82.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       39.9843  -99.0000 -120.0000 86

 23 omega    6.00  119.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       39.9843   77.0000 -180.0000 113

 24 omega   72.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   77.0000   60.0000 106

 25 omega   75.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   30.0000  150.0000 103

 26 omega   78.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   45.0000 -150.0000 100
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1030229000
_diffrn_orient_matrix_UB_12      -0.0397462000
_diffrn_orient_matrix_UB_13      -0.0614895000
_diffrn_orient_matrix_UB_21      -0.0881978000
_diffrn_orient_matrix_UB_22      0.0446428000
_diffrn_orient_matrix_UB_23      0.0724266000
_diffrn_orient_matrix_UB_31      -0.0013264000
_diffrn_orient_matrix_UB_32      0.1217070000
_diffrn_orient_matrix_UB_33      -0.0465422000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0768
_diffrn_reflns_av_unetI/netI     0.0336
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            20872
_diffrn_reflns_theta_full        73.61
_diffrn_reflns_theta_max         73.61
_diffrn_reflns_theta_min         4.94
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.964
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.15591
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.307
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             776
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.329
_refine_diff_density_min         -0.390
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.01(2)
_refine_ls_extinction_coef       0.0045(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     239
_refine_ls_number_reflns         3725
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.122
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0478
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0793P)^2^+0.4163P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1311
_refine_ls_wR_factor_ref         0.1361
_reflns_number_gt                3458
_reflns_number_total             3725
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c6ob02160c2.cif
_cod_data_source_block           g151231a
_cod_depositor_comments
'Adding full bibliography for 7155321--7155323.cif.'
_cod_original_cell_volume        1879.28(9)
_cod_database_code               7155322
_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 C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C1, C2, C3, C4, C5, C6
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6: within 1.7A with sigma of
0.003 and sigma for terminal atoms of 0.01
4.a Ternary CH refined with riding coordinates:
 C7(H7)
4.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C12(H12), C13(H13), C14(H14), C15(H15)
4.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_olex2_date_sample_data_collection 2015-12-31
_olex2_submission_special_instructions 'No special instructions were received'