Efficient access to chiral dihydrobenzoxazinones via Rh-catalyzed hydrogenation
Chen, Ziyi; Yin, Xuguang; Dong, Xiu-Qin; Zhang, Xumu; RSC Advances 9 (2019) 15466–; doi:10.1039/C9RA02694K

data_7232801
_publ_section_title
;
 Efficient access to chiral dihydrobenzoxazinones via Rh-catalyzed
 hydrogenation
;
_journal_issue                   27
_journal_name_full               'RSC Advances'
_journal_page_first              15466
_journal_paper_doi               10.1039/C9RA02694K
_journal_volume                  9
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C12 H12 Cl N O4'
_chemical_formula_sum            'C12 H12 Cl N O4'
_chemical_formula_weight         269.68
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-02-28
_audit_creation_method
; 
Olex2 1.2 
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506) 
;
_audit_update_record
;
2019-03-26 deposited with the CCDC.    2019-05-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.268(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.2919(11)
_cell_length_b                   28.317(6)
_cell_length_c                   8.7074(19)
_cell_measurement_reflns_used    1288
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      20.22
_cell_measurement_theta_min      2.40
_cell_volume                     1270.0(5)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'Bruker APEX2'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296(2)
_diffrn_measured_fraction_theta_full 0.953
_diffrn_measured_fraction_theta_max 0.953
_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  0.0237
_diffrn_reflns_av_unetI/netI     0.0511
_diffrn_reflns_Laue_measured_fraction_full 0.953
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            5933
_diffrn_reflns_point_group_measured_fraction_full 0.744
_diffrn_reflns_point_group_measured_fraction_max 0.744
_diffrn_reflns_theta_full        25.057
_diffrn_reflns_theta_max         25.057
_diffrn_reflns_theta_min         2.403
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.306
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.7076
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
SADABS-2008/1 (Bruker,2008) was used for absorption correction. 
wR2(int) was 0.1469 before and 0.0455 after correction. 
The Ratio of minimum to maximum transmission is 0.9493. 
The \l/2 correction factor is 0.0015. 
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.410
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             560
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.152
_refine_diff_density_min         -0.147
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
; 
 Flack x determined using 616 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.05(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     385
_refine_ls_number_reflns         3363
_refine_ls_number_restraints     83
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0834
_refine_ls_R_factor_gt           0.0444
_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^)+(0.0336P)^2^+0.1678P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0835
_refine_ls_wR_factor_ref         0.0992
_reflns_Friedel_coverage         0.527
_reflns_Friedel_fraction_full    0.526
_reflns_Friedel_fraction_max     0.526
_reflns_number_gt                2179
_reflns_number_total             3363
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ra02694k2.cif
_cod_data_source_block           t
_cod_database_code               7232801
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.970
_olex2_refinement_description
; 
1. Fixed Uiso 
 At 1.2 times of: 
  All C(H) groups, All C(H,H) groups, All N(H) groups 
 At 1.5 times of: 
  All C(H,H,H) groups 
2. Restrained distances 
 O4A-C11A = O4-C11 
 1.45 with sigma of 0.01 
 C12-C11 = C12A-C11A 
 1.51 with sigma of 0.01 
 C24-C23 = C24A-C23A 
 1.51 with sigma of 0.01 
 O8A-C23A = O8-C23 
 1.45 with sigma of 0.01 
 O4A-C10 \\sim O4-C10 
 with sigma of 0.01 
 O8A-C22 \\sim O8-C22 
 with sigma of 0.01 
3. Uiso/Uaniso restraints and constraints 
Uanis(O4) \\sim Ueq, Uanis(O4A) \\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C11) 
\\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C12A) \\sim Ueq: with sigma of 0.01 and 
sigma for terminal atoms of 0.02 
Uanis(O8A) \\sim Ueq, Uanis(O8) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C23) 
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C24A) \\sim Ueq: with sigma of 0.01 and 
sigma for terminal atoms of 0.02 
4. Others 
 Sof(O4A)=Sof(C11A)=Sof(H11C)=Sof(H11D)=Sof(C12A)=Sof(H12D)=Sof(H12E)= 
 Sof(H12F)=1-FVAR(1) 
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(O4)= 
 FVAR(1) 
 Sof(O8A)=Sof(C23A)=Sof(H23C)=Sof(H23D)=Sof(C24A)=Sof(H24D)=Sof(H24E)= 
 Sof(H24F)=1-FVAR(2) 
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(O8)= 
 FVAR(2) 
5.a Ternary CH refined with riding coordinates: 
 C8(H8), C20(H20) 
5.b Secondary CH2 refined with riding coordinates: 
 C9(H9A,H9B), C11(H11A,H11B), C21(H21A,H21B), C23(H23A,H23B), C11A(H11C,H11D), 
 C23A(H23C,H23D) 
5.c Aromatic/amide H refined with riding coordinates: 
 C2(H2), C5(H5), C6(H6), N1(H1), C14(H14), C17(H17), C18(H18), N2(H2A) 
5.d Idealised Me refined as rotating group: 
 C12(H12A,H12B,H12C), C24(H24A,H24B,H24C), C12A(H12D,H12E,H12F), C24A(H24D, 
 H24E,H24F) 
;
_olex2_submission_special_instructions 'No special instructions were received'