Enantioselective Palladium-Catalyzed Diboration of 1,1-Disubstituted Allenes
Tang, Wenjun; Liu, Jiawang; Nie, Ming; Zhou, Qing-Hai; Gao, Shen; Jiang, Wenhao; Chung, Lung Wa; Ding, Kuiling; Chem. Sci.  (2017) –; doi:10.1039/C7SC01254C

data_1546041
_publ_section_title
;
 Enantioselective Palladium-Catalyzed Diboration of 1,1-Disubstituted
 Allenes
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC01254C
_journal_year                    2017
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C18 H18 Cl N3 O'
_chemical_formula_sum            'C18 H18 Cl N3 O'
_chemical_formula_weight         327.80
_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     dual
_audit_creation_date             2016-10-28
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2016-11-16 deposited with the CCDC.
2017-05-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.443(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.6963(15)
_cell_length_b                   7.8375(10)
_cell_length_c                   18.213(2)
_cell_measurement_reflns_used    3855
_cell_measurement_temperature    130
_cell_measurement_theta_max      25.822
_cell_measurement_theta_min      2.69
_cell_volume                     1659.0(4)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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  0.0321
_diffrn_reflns_av_unetI/netI     0.0603
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            16974
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.618
_diffrn_reflns_theta_min         1.125
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.238
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6819
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1200 before and 0.0445 after correction.
The Ratio of minimum to maximum transmission is 0.9140.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.312
_exptl_crystal_description       block
_exptl_crystal_F_000             688
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.240
_refine_diff_density_min         -0.302
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Flack x determined using 2613 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     419
_refine_ls_number_reflns         9757
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0693
_refine_ls_R_factor_gt           0.0464
_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^)+(0.0368P)^2^+0.1709P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0871
_refine_ls_wR_factor_ref         0.0972
_reflns_Friedel_coverage         0.799
_reflns_Friedel_fraction_full    0.945
_reflns_Friedel_fraction_max     0.908
_reflns_number_gt                7532
_reflns_number_total             9757
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc01254c2.cif
_cod_data_source_block           mo_dm16701_0m
_cod_database_code               1546041
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.965
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2), C20(H20)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C24(H24A,H24B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C8(H8), C9(H9), C11(H11), C12(H12), C14(H14), C15(H15),
 C16(H16), C17(H17), C18(H18), C22(H22), C23(H23), C26(H26), C27(H27), C29(H29),
  C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36)
2.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C21(H21A,H21B,H21C)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2A)
;
_shelx_res_checksum              47769
_shelx_shelxl_version_number     2016/6
_olex2_submission_special_instructions 'No special instructions were received'