Catalytic, Asymmetric Dearomative Synthesis of Complex Cyclohexanes via a Highly Regio- and Stereoselective Arene Cyclopropanation Using α-Cyanodiazoacetates
Smith, Kendrick L.; Padgett, Cody L.; Mackay, William D.; Johnson, Jeffrey S.; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.9b13080

data_4134589
_publ_section_title
;
 Catalytic, Asymmetric Dearomative Synthesis of Complex Cyclohexanes via a
 Highly Regio- and Stereoselective Arene Cyclopropanation Using
 \a-Cyanodiazoacetates
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b13080
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H22 N4 O4'
_chemical_formula_sum            'C22 H22 N4 O4'
_chemical_formula_weight         406.43
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.26220(10)
_cell_length_b                   10.00390(10)
_cell_length_c                   31.7656(5)
_cell_measurement_reflns_used    9919
_cell_measurement_temperature    100
_cell_measurement_theta_max      66.55
_cell_measurement_theta_min      2.78
_cell_volume                     1990.00(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      100
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0232
_diffrn_reflns_av_unetI/netI     0.0107
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            33282
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        66.575
_diffrn_reflns_theta_max         66.575
_diffrn_reflns_theta_min         2.782
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.784
_exptl_absorpt_correction_T_max  0.9557
_exptl_absorpt_correction_T_min  0.8381
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0565 before and 0.0384 after correction. The Ratio of minimum to maximum transmission is 0.8769. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.357
_exptl_crystal_description       block
_exptl_crystal_F_000             856
_exptl_crystal_size_max          0.385
_exptl_crystal_size_mid          0.134
_exptl_crystal_size_min          0.125
_refine_diff_density_max         0.171
_refine_diff_density_min         -0.181
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 1410 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.960
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     275
_refine_ls_number_reflns         3490
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.960
_refine_ls_R_factor_all          0.0289
_refine_ls_R_factor_gt           0.0286
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0981
_refine_ls_wR_factor_ref         0.0988
_reflns_Friedel_coverage         0.702
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                3446
_reflns_number_total             3490
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13080_si_001.cif
_cod_data_source_block           kls_7_3_2018
_cod_database_code               4134589
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.908
_shelx_estimated_absorpt_t_min   0.752
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11)
2.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22)
2.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              88182
_shelx_hkl_checksum              36906
_olex2_submission_special_instructions 'No special instructions were received'