Asymmetric Darzens Reaction of Isatins with Diazoacetamides Catalyzed by Chiral BINOL-Titanium Complex.
Chai, Guo-Li; Han, Jian-Wei; Wong, Henry N. C.; The Journal of organic chemistry 82 (2017) 12647–12654; doi:10.1021/acs.joc.7b02439

data_4033030
_publ_section_title
;
 Asymmetric Darzens Reaction of Isatins with Diazoacetamides Catalyzed by
 Chiral BINOL-Titanium Complex.
;
_journal_issue                   23
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12647
_journal_page_last               12654
_journal_paper_doi               10.1021/acs.joc.7b02439
_journal_volume                  82
_journal_year                    2017
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C23 H17 I N2 O3'
_chemical_formula_sum            'C23 H17 I N2 O3'
_chemical_formula_weight         496.28
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-03-20
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5324)
;
_cell_angle_alpha                72.387(3)
_cell_angle_beta                 88.787(3)
_cell_angle_gamma                85.279(4)
_cell_formula_units_Z            2
_cell_length_a                   4.9377(8)
_cell_length_b                   11.3507(19)
_cell_length_c                   18.673(3)
_cell_measurement_reflns_used    2627
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      25.215
_cell_measurement_theta_min      2.29
_cell_volume                     994.1(3)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      296
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0260
_diffrn_reflns_av_unetI/netI     0.0824
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            10041
_diffrn_reflns_point_group_measured_fraction_full 0.685
_diffrn_reflns_point_group_measured_fraction_max 0.644
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.606
_diffrn_reflns_theta_min         1.888
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.638
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6323
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1108 before and 0.0375 after correction. The Ratio of minimum to maximum transmission is 0.8475. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.658
_exptl_crystal_description       prism
_exptl_crystal_F_000             492
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.894
_refine_diff_density_min         -0.723
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.015(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.922
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     523
_refine_ls_number_reflns         7880
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      0.922
_refine_ls_R_factor_all          0.0982
_refine_ls_R_factor_gt           0.0407
_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^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0456
_refine_ls_wR_factor_ref         0.0569
_reflns_Friedel_coverage         0.310
_reflns_Friedel_fraction_full    0.371
_reflns_Friedel_fraction_max     0.305
_reflns_number_gt                4719
_reflns_number_total             7880
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b02439_si_001.cif
_cod_data_source_block           mo_dm17171_0m
_cod_depositor_comments
'Adding full bibliography for 4033030--4033031.cif.'
_cod_database_code               4033030
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.791
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C32(H32)
2.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C40(H40A,H40B)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C2(H2A), C3(H3), C5(H5), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), N4(H4), C25(H25),
 C26(H26), C28(H28), C35(H35), C36(H36), C37(H37), C38(H38), C39(H39), C42(H42),
  C43(H43), C44(H44), C45(H45), C46(H46)
;
_shelx_res_checksum              78784
_shelx_hkl_checksum              76146
_olex2_submission_special_instructions 'No special instructions were received'