Chemoenzymatic Total Synthesis of Hydromorphone by an Oxidative Dearomatization/Intramolecular [4 + 2] Cycloaddition Sequence: A Second-Generation Approach.
Rycek, Lukas; Hayward, John J.; Latif, Marwa Abdel; Tanko, James; Simionescu, Razvan; Hudlicky, Tomas; The Journal of organic chemistry 81 (2016) 10930–10941; doi:10.1021/acs.joc.6b01990

data_4037324
_publ_section_title
;
 Chemoenzymatic Total Synthesis of Hydromorphone by an Oxidative
 Dearomatization/Intramolecular [4 + 2] Cycloaddition Sequence: A
 Second-Generation Approach.
;
_journal_issue                   22
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10930
_journal_page_last               10941
_journal_paper_doi               10.1021/acs.joc.6b01990
_journal_volume                  81
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H23 Br O4'
_chemical_formula_sum            'C22 H23 Br O4'
_chemical_formula_weight         431.31
_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   geom
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 98.6290(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.2978(2)
_cell_length_b                   14.6967(3)
_cell_length_c                   18.4170(4)
_cell_measurement_reflns_used    9837
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      30.01
_cell_measurement_theta_min      2.63
_cell_volume                     1952.93(8)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      173(2)
_diffrn_measured_fraction_theta_full 0.999
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0252
_diffrn_reflns_av_unetI/netI     0.0219
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            55479
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.550
_diffrn_reflns_theta_min         1.118
_exptl_absorpt_coefficient_mu    2.130
_exptl_absorpt_correction_T_max  0.7325
_exptl_absorpt_correction_T_min  0.04761
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.467
_exptl_crystal_description       block
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.468
_exptl_crystal_size_mid          0.302
_exptl_crystal_size_min          0.234
_refine_diff_density_max         0.378
_refine_diff_density_min         -0.332
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
; 
 Refined as an inversion twin. 
;
_refine_ls_abs_structure_Flack   0.457(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     514
_refine_ls_number_reflns         11926
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0427
_refine_ls_R_factor_gt           0.0313
_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^)+(0.0458P)^2^+0.2958P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0771
_refine_ls_wR_factor_ref         0.0819
_reflns_Friedel_coverage         0.932
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                9872
_reflns_number_total             11926
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b01990_si_003.cif
_cod_data_source_block           pbrbn_0m_b
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4037324
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.436
_shelx_estimated_absorpt_t_max   0.636
_shelx_res_checksum              7549
_shelx_hkl_checksum              73444