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_7155321
_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         'C22 H19 Cl N O3'
_chemical_formula_sum            'C22 H19 Cl N O3'
_chemical_formula_weight         380.83
_chemical_name_systematic
'(1S,1R,6R)-tert-butyl 6'-chloro-2'-oxo-6,6a-dihydro-1H-spiro[cyclopropa[a]indene-1,3'-indoline]-1'-carboxylate'
_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             2015-12-24
_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                   7.3670(3)
_cell_length_b                   12.1881(3)
_cell_length_c                   21.7372(5)
_cell_measurement_reflns_used    5148
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.7470
_cell_measurement_theta_min      3.6620
_cell_volume                     1951.78(10)
_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
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
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 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_details
;
  1 omega  -41.00   36.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.1093   37.0000  -30.0000 77

  2 omega  -48.00   35.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.1093   37.0000   90.0000 83

  3 omega  -31.00    5.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.1093   37.0000 -180.0000 36

  4 omega   -2.00   25.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.1093  -99.0000  -60.0000 27

  5 omega   25.00   51.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.1093 -125.0000   30.0000 26

  6 omega   46.00   85.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -30.0000  150.0000 39

  7 omega  107.00  175.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  111.0000 -180.0000 68

  8 omega   31.00   60.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -30.0000  -30.0000 29

  9 omega   41.00   95.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -45.0000 -150.0000 54

 10 omega   33.00   92.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -45.0000  120.0000 59

 11 omega  107.00  173.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  111.0000   90.0000 66

 12 omega   56.00   91.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -30.0000  -90.0000 35

 13 omega  105.00  175.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   61.0000  -90.0000 70

 14 omega -114.00  -11.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.1093  -57.0000  -90.0000 103

 15 omega -114.00  -10.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.1093  -60.0000   13.0000 104

 16 omega -114.00  -11.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.1093  -57.0000 -180.0000 103

 17 omega   75.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   30.0000    0.0000 103

 18 omega   28.00  116.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522 -111.0000  150.0000 88

 19 omega   75.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   30.0000 -120.0000 103

 20 omega   45.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   15.0000  150.0000 133
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0975918000
_diffrn_orient_matrix_UB_12      -0.0106885000
_diffrn_orient_matrix_UB_13      -0.0623841000
_diffrn_orient_matrix_UB_21      -0.1351217000
_diffrn_orient_matrix_UB_22      -0.0900210000
_diffrn_orient_matrix_UB_23      -0.0194979000
_diffrn_orient_matrix_UB_31      -0.1261330000
_diffrn_orient_matrix_UB_32      0.0880763000
_diffrn_orient_matrix_UB_33      -0.0274884000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0365
_diffrn_reflns_av_unetI/netI     0.0246
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            15887
_diffrn_reflns_theta_full        73.67
_diffrn_reflns_theta_max         73.67
_diffrn_reflns_theta_min         4.07
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.909
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42467
_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    1.296
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             796
_exptl_crystal_size_max          0.3500
_exptl_crystal_size_mid          0.2500
_exptl_crystal_size_min          0.1500
_refine_diff_density_max         0.281
_refine_diff_density_min         -0.234
_refine_diff_density_rms         0.047
_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_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     277
_refine_ls_number_reflns         3871
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0577
_refine_ls_R_factor_gt           0.0474
_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^)+(0.1000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1366
_refine_ls_wR_factor_ref         0.1482
_reflns_number_gt                3257
_reflns_number_total             3871
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c6ob02160c2.cif
_cod_data_source_block           g151224a
_cod_depositor_comments
'Adding full bibliography for 7155321--7155323.cif.'
_cod_original_cell_volume        1951.79(10)
_cod_database_code               7155321
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C20, C21, C22, C20A, C21A, C22A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
3. Uiso/Uaniso restraints and constraints
C20 \\sim C21 \\sim C22 \\sim C20A \\sim C21A \\sim C22A: within 1.7A with
sigma of 0.002 and sigma for terminal atoms of 0.004
4. Others
 Fixed Sof: C20(0.5) H20A(0.5) H20B(0.5) H20C(0.5) C20A(0.5) H20D(0.5)
 H20E(0.5) H20F(0.5) C21(0.5) H21A(0.5) H21B(0.5) H21C(0.5) C21A(0.5) H21D(0.5)
 H21E(0.5) H21F(0.5) C22(0.5) H22A(0.5) H22B(0.5) H22C(0.5) C22A(0.5) H22D(0.5)
 H22E(0.5) H22F(0.5)
5.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C9(H9), C12(H12), C13(H13), C15(H15)
5.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F), C21(H21A,H21B,H21C), C21A(H21D,
 H21E,H21F), C22(H22A,H22B,H22C), C22A(H22D,H22E,H22F)
;
_olex2_date_sample_data_collection 2015-12-24
_olex2_submission_special_instructions 'No special instructions were received'