Rhodium(III)-Catalyzed Asymmetric Borylative Cyclization of Cyclohexadienone-Containing 1,6-Dienes: An Experimental and DFT Study.
Tan, Yun-Xuan; Zhang, Fang; Xie, Pei-Pei; Zhang, Shuo-Qing; Wang, Yi-Fan; Li, Qing-Hua; Tian, Ping; Hong, Xin; Lin, Guo-Qiang; Journal of the American Chemical Society 141 (2019) 12770–12779; doi:10.1021/jacs.9b05583

data_4127755
_publ_section_title
;
 Rhodium(III)-Catalyzed Asymmetric Borylative Cyclization of
 Cyclohexadienone-Containing 1,6-Dienes: An Experimental and DFT Study.
;
_journal_issue                   32
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12770
_journal_page_last               12779
_journal_paper_doi               10.1021/jacs.9b05583
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C16 H27 B O4'
_chemical_formula_sum            'C16 H27 B O4'
_chemical_formula_weight         294.18
_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             2018-06-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.957(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.2022(2)
_cell_length_b                   12.0562(5)
_cell_length_c                   11.3655(4)
_cell_measurement_reflns_used    5924
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      54.59
_cell_measurement_theta_min      9.344
_cell_volume                     848.72(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      296
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0408
_diffrn_reflns_av_unetI/netI     0.0419
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            9311
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.965
_diffrn_reflns_theta_min         9.341
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.411
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.4972
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1598 before and 0.0622 after correction. The Ratio of minimum to maximum transmission is 0.6622. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.151
_exptl_crystal_description       block
_exptl_crystal_F_000             320
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.596
_refine_diff_density_min         -0.249
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 1084 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.05(14)
_refine_ls_extinction_coef       0.09(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     197
_refine_ls_number_reflns         3123
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0893
_refine_ls_R_factor_gt           0.0811
_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^)+(0.1100P)^2^+0.5000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2034
_refine_ls_wR_factor_ref         0.2113
_reflns_Friedel_coverage         0.889
_reflns_Friedel_fraction_full    0.961
_reflns_Friedel_fraction_max     0.958
_reflns_number_gt                2725
_reflns_number_total             3123
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05583_si_006.cif
_cod_data_source_block           mjr18062_0m
_cod_database_code               4127755
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.941
_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(H2A), C3(H3), C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C8(H8A,H8B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C16(H16A,H16B,H16C)
2.e Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              6916
_shelx_hkl_checksum              43414
_olex2_submission_special_instructions 'No special instructions were received'