Photocatalytic carbanion generation – benzylation of aliphatic aldehydes to secondary alcohols
Donabauer, Karsten; Maity, Mitasree; Berger, Anna Lucia; Huff, Gregory S.; Crespi, Stefano; König, Burkhard; Chemical Science  (2019) –; doi:10.1039/C9SC01356C

data_1550942
_publ_section_title
;
 Photocatalytic carbanion generation -- benzylation of aliphatic aldehydes
 to secondary alcohols
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC01356C
_journal_year                    2019
_chemical_formula_moiety         'C62 H39 N5, C4 H8 O2'
_chemical_formula_sum            'C66 H47 N5 O2'
_chemical_formula_weight         942.08
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc218fvm
_audit_creation_date             2018-12-13
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_audit_update_record
;
2018-12-13 deposited with the CCDC.    2019-04-25 downloaded from the CCDC.
;
_cell_angle_alpha                74.949(3)
_cell_angle_beta                 83.485(3)
_cell_angle_gamma                69.462(3)
_cell_formula_units_Z            2
_cell_length_a                   13.2060(4)
_cell_length_b                   14.1214(4)
_cell_length_c                   14.4666(5)
_cell_measurement_reflns_used    12463
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      73.6850
_cell_measurement_theta_min      4.0270
_cell_volume                     2438.95(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.37b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.37b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.37b (Rigaku OD, 2017)'
_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_environment      N~2~
_diffrn_ambient_temperature      123.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1773
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -70.00  31.00   1.00   10.00    --  -41.95  57.00 120.00  101
  2  \w   -114.00 -14.00   1.00   10.00    --  -41.95 -57.00 -30.00  100
  3  \w    -20.00  83.00   1.00   10.00    --   41.95 -99.00-120.00  103
  4  \w     54.00 158.00   1.00   47.50    --  106.55  15.00  30.00  104
  5  \w     33.00 122.00   1.00   47.50    --  106.55-125.00 -30.00   89
  6  \w     54.00 158.00   1.00   47.50    --  106.55  15.00 120.00  104
  7  \w     30.00  69.00   1.00   47.50    --  106.55 -30.00 120.00   39
  8  \w     33.00 122.00   1.00   47.50    --  106.55-125.00 150.00   89
  9  \w     30.00  69.00   1.00   47.50    --  106.55 -30.00  90.00   39
 10  \w     34.00  77.00   1.00   47.50    --  106.55 -45.00 -30.00   43
 11  \w     30.00  69.00   1.00   47.50    --  106.55 -30.00-180.00   39
 12  \w     30.00  69.00   1.00   47.50    --  106.55 -30.00 150.00   39
 13  \w     30.00 139.00   1.00   47.50    --  106.55 -77.00 -30.00  109
 14  \w     30.00 139.00   1.00   47.50    --  106.55 -77.00 150.00  109
 15  \w   -118.00  -9.00   1.00   10.00    --  -41.95 -77.00 -90.00  109
 16  \w   -114.00 -14.00   1.00   10.00    --  -41.95 -57.00  90.00  100
 17  \w   -114.00 -14.00   1.00   10.00    --  -41.95 -57.00-180.00  100
 18  \w     30.00  69.00   1.00   47.50    --  106.55 -30.00 -90.00   39
 19  \w     77.00 158.00   1.00   47.50    --  106.55  61.00 -90.00   81
 20  \w     74.00 158.00   1.00   47.50    --  106.55  77.00 120.00   84
 21  \w     74.00 158.00   1.00   47.50    --  106.55  77.00   0.00   84
 22  \w     74.00 158.00   1.00   47.50    --  106.55  77.00-150.00   84
 23  \w     54.00 158.00   1.00   47.50    --  106.55  15.00-120.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0415227000
_diffrn_orient_matrix_UB_12      0.0136131000
_diffrn_orient_matrix_UB_13      0.0893754000
_diffrn_orient_matrix_UB_21      0.0887653000
_diffrn_orient_matrix_UB_22      -0.1074078000
_diffrn_orient_matrix_UB_23      0.0097808000
_diffrn_orient_matrix_UB_31      0.0769731000
_diffrn_orient_matrix_UB_32      0.0515075000
_diffrn_orient_matrix_UB_33      -0.0639074000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0253
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            27888
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.869
_diffrn_reflns_theta_min         3.440
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.610
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.720
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.37b (Rigaku Oxford Diffraction, 2017)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_description       plate
_exptl_crystal_F_000             988
_exptl_crystal_size_max          0.211
_exptl_crystal_size_mid          0.159
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.704
_refine_diff_density_min         -0.476
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     660
_refine_ls_number_reflns         9563
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0577P)^2^+1.0165P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1087
_refine_ls_wR_factor_ref         0.1162
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8127
_reflns_number_total             9563
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01356c2.cif
_cod_data_source_block           r121
_cod_original_cell_volume        2438.95(15)
_cod_database_code               1550942
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C62 H39 N5'
_chemical_oxdiff_usercomment     Donabauer_Koenig_DR338
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.882
_reflns_odcompleteness_completeness 99.54
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
2.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C65(H65A,H65B)
2.b Aromatic/amide H refined with riding coordinates:
 C62(H62), C31(H31), C58(H58), C59(H59), C38(H38), C50(H50), C26(H26),
 C55(H55), C19(H19), C47(H47), C43(H43), C32(H32), C10(H10), C56(H56), C34(H34),
  C49(H49), C57(H57), C37(H37), C61(H61), C14(H14), C60(H60), C35(H35),
 C36(H36), C23(H23), C48(H48), C33(H33), C20(H20), C46(H46), C24(H24), C44(H44),
  C25(H25), C11(H11), C13(H13), C12(H12), C45(H45), C21(H21), C22(H22)
2.c Idealised Me refined as rotating group:
 C63(H63A,H63B,H63C), C66(H66A,H66B,H66C)
;
_olex2_date_sample_data_collection 2018-12-11
_olex2_date_sample_submission    2018-12-11
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems CryoStream 700'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder oil'
_olex2_submission_original_sample_id DR338
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.521
_oxdiff_exptl_absorpt_empirical_full_min 0.630