Functionalization of Deutero- and Protoporphyrin IX Dimethyl Esters via Palladium-Catalyzed Coupling Reactions.
O'Brien, Jessica M; Sitte, Elisabeth; Flanagan, Keith J.; Kühner, Hannes; Hallen, Lukas J.; Gibbons, Dáire; Senge, Mathias O.; The Journal of organic chemistry 84 (2019) 6158–6173; doi:10.1021/acs.joc.9b00350

data_4033683
_publ_section_title
;
 Functionalization of Deutero- and Protoporphyrin IX Dimethyl Esters via
 Palladium-Catalyzed Coupling Reactions.
;
_journal_issue                   10
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              6158
_journal_page_last               6173
_journal_paper_doi               10.1021/acs.joc.9b00350
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C38 H42 N4 O4'
_chemical_formula_sum            'C38 H42 N4 O4'
_chemical_formula_weight         618.75
_chemical_name_systematic
'3,8-Diallyl-deuteroporphyrin IX dimethyl ester'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                72.555(7)
_cell_angle_beta                 74.384(5)
_cell_angle_gamma                75.547(4)
_cell_formula_units_Z            2
_cell_length_a                   8.7165(15)
_cell_length_b                   14.056(3)
_cell_length_c                   14.557(3)
_cell_measurement_reflns_used    4458
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.11
_cell_measurement_theta_min      2.41
_cell_volume                     1610.8(6)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0771
_diffrn_reflns_av_unetI/netI     0.0711
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            35315
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.533
_diffrn_reflns_theta_min         1.500
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              graphite-monochromated
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.083
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6447
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0756 before and 0.0652 after correction. The Ratio of minimum to maximum transmission is 0.8651. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.276
_exptl_crystal_description       square
_exptl_crystal_F_000             660
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.640
_refine_diff_density_min         -0.391
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     467
_refine_ls_number_reflns         5921
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.1305
_refine_ls_R_factor_gt           0.0838
_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^)+(0.1127P)^2^+3.3518P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2295
_refine_ls_wR_factor_ref         0.2582
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3705
_reflns_number_total             5921
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00350_si_002.cif
_cod_data_source_block           dgib011x
_cod_original_cell_volume        1610.8(5)
_cod_database_code               4033683
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.975
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C83-C82 = C33A-C32 = C33-C32
 1.2 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
O1: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
C133: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
C134 \\sim C13A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
O1 \\sim O1A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: H32(0.55) H32A(0.45) H82(0.55) H82A(0.45) O1(0.54) O2(0.54)
 C33(0.55) H33A(0.55) H33B(0.55) C83(0.55) H83A(0.55) H83B(0.55) C134(0.54)
 H13E(0.54) H13F(0.54) H13G(0.54) O1A(0.46) O2A(0.46) C13A(0.46) H13H(0.46)
 H13I(0.46) H13J(0.46) C33A(0.45) H33C(0.45) H33D(0.45) C83A(0.45) H83C(0.45)
 H83D(0.45)
5.a Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C81(H81A,H81B), C131(H13A,H13B), C132(H13C,H13D), C171(H17A,
 H17B), C172(H17C,H17D)
5.b Aromatic/amide H refined with riding coordinates:
 N21(H21), N23(H23), C5(H5), C10(H10), C15(H15), C20(H20), C32(H32), C32(H32A),
  C82(H82), C82(H82A)
5.c X=CH2 refined with riding coordinates:
 C33(H33A,H33B), C83(H83A,H83B), C33A(H33C,H33D), C83A(H83C,H83D)
5.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C71(H71A,H71B,H71C), C121(H12A,H12B,H12C), C174(H17E,
 H17F,H17G), C181(H18A,H18B,H18C), C134(H13E,H13F,H13G), C13A(H13H,H13I,H13J)
;
_shelx_res_checksum              39281
_shelx_hkl_checksum              64010
_olex2_submission_special_instructions 'No special instructions were received'