Well-Designed Phosphine-Urea Ligand for Highly Diastereo- and Enantioselective 1,3-Dipolar Cycloaddition of Methacrylonitrile: A Combined Experimental and Theoretical Study.
Xiong, Yang; Du, Zhuanzhuan; Chen, Haohua; Yang, Zhao; Tan, Qiuyuan; Zhang, Changhui; Zhu, Lei; Lan, Yu; Zhang, Min; Journal of the American Chemical Society 141 (2019) 961–971; doi:10.1021/jacs.8b10939

data_4133550
_publ_section_title
;
 Well-Designed Phosphine-Urea Ligand for Highly Diastereo- and
 Enantioselective 1,3-Dipolar Cycloaddition of Methacrylonitrile: A
 Combined Experimental and Theoretical Study.
;
_journal_issue                   2
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              961
_journal_page_last               971
_journal_paper_doi               10.1021/jacs.8b10939
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C13 H13 Br N2 O2'
_chemical_formula_sum            'C13 H13 Br N2 O2'
_chemical_formula_weight         309.16
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-04-01
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.754(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.4672(6)
_cell_length_b                   5.7450(3)
_cell_length_c                   11.4377(7)
_cell_measurement_reflns_used    2477
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      22.6980
_cell_measurement_theta_min      3.6180
_cell_volume                     643.16(7)
_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_temperature      295(2)
_diffrn_detector_area_resol_mean 16.0892
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0496
_diffrn_reflns_av_unetI/netI     0.0569
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            8604
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.363
_diffrn_reflns_theta_min         3.637
_diffrn_source                   'micro-focus sealed X-ray tube'
_exptl_absorpt_coefficient_mu    3.191
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71622
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41k (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.596
_exptl_crystal_description       Block
_exptl_crystal_F_000             312
_exptl_crystal_size_max          0.50
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.422
_refine_diff_density_min         -0.272
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 577 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.019(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     168
_refine_ls_number_reflns         2612
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0800
_refine_ls_R_factor_gt           0.0454
_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^)+(0.0408P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0861
_refine_ls_wR_factor_ref         0.0995
_reflns_Friedel_coverage         0.813
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                1820
_reflns_number_total             2612
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b10939_si_003.cif
_cod_data_source_block           xy-3
_cod_database_code               4133550
_shelx_shelxl_version_number     2014/7
_oxdiff_exptl_absorpt_empirical_full_min 0.735
_oxdiff_exptl_absorpt_empirical_full_max 1.291
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_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.a Ternary CH refined with riding coordinates:
 C5(H5), C7(H7), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C10(H10), C9(H9), C13(H13)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_olex2_submission_special_instructions 'No special instructions were received'