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_4037325
_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_formula_moiety         'C16 H18 O4'
_chemical_formula_sum            'C16 H18 O4'
_chemical_formula_weight         274.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 107.733(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.9547(16)
_cell_length_b                   9.8218(14)
_cell_length_c                   11.9089(15)
_cell_measurement_reflns_used    5113
_cell_measurement_temperature    147(2)
_cell_measurement_theta_max      27.12
_cell_measurement_theta_min      2.74
_cell_volume                     1331.9(3)
_computing_cell_refinement       APEX2
_computing_data_collection       'APEX2 (Bruker, 2014)'
_computing_data_reduction        'SAINT (Bruker, 2014)'
_computing_molecular_graphics    'PLATON (Spek, 2009)'
_computing_publication_material  'SHELXTL (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      147(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker Kappa APEX-DUO CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0422
_diffrn_reflns_av_unetI/netI     0.0319
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            21714
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.580
_diffrn_reflns_theta_min         1.788
_diffrn_source                   'sealed tube with Bruker Triumph monochromator'
_exptl_absorpt_coefficient_mu    0.098
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.7181
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Bruker 2014)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.368
_exptl_crystal_description       Block
_exptl_crystal_F_000             584
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.260
_exptl_crystal_size_min          0.180
_refine_diff_density_max         0.278
_refine_diff_density_min         -0.244
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     182
_refine_ls_number_reflns         3087
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0593
_refine_ls_R_factor_gt           0.0378
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0377P)^2^+0.5179P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0829
_refine_ls_wR_factor_ref         0.0945
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2326
_reflns_number_total             3087
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b01990_si_001.cif
_cod_data_source_block           d1684
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               4037325
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.971
_shelx_estimated_absorpt_t_max   0.983
_shelx_res_checksum              25926
_shelx_hkl_checksum              5280