Light-triggered Catalytic Asymmetric Allylic Benzylation with Photogenerated C-Nucleophiles.
Paria, Suva; Carletti, Edoardo; Marcon, Michela; Cherubini-Celli, Alessio; Mazzanti, Andrea; Rancan, Marzio; Dell'Amico, Luca; Bonchio, Marcella; Companyó, Xavier; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00175

data_4038015
_publ_section_title
;
 Light-triggered Catalytic Asymmetric Allylic Benzylation with
 Photogenerated C-Nucleophiles.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00175
_journal_year                    2020
_chemical_formula_moiety         'C H2 Cl2, C27 H23 N O4'
_chemical_formula_sum            'C28 H25 Cl2 N O4'
_chemical_formula_weight         510.39
_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             2020-01-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                74.989(3)
_cell_angle_beta                 74.857(3)
_cell_angle_gamma                69.550(4)
_cell_formula_units_Z            2
_cell_length_a                   8.7462(3)
_cell_length_b                   11.3434(5)
_cell_length_c                   14.7196(5)
_cell_measurement_reflns_used    11468
_cell_measurement_temperature    296.4(6)
_cell_measurement_theta_max      26.0760
_cell_measurement_theta_min      2.6250
_cell_volume                     1297.90(9)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 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_environment      air
_diffrn_ambient_temperature      296.4(6)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1274
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.898
_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    -90.00 -33.00   1.00   10.00    --  -18.52 148.00 107.41   57
  2  \w    -12.00  89.00   1.00   10.00    --   18.52  77.00  30.00  101
  3  \w    -50.00  40.00   1.00   10.00    --   18.52 -57.00-120.00   90
  4  \w     34.00  95.00   1.00   10.00    --   18.52 179.00-180.00   61
  5  \w     -3.00  87.00   1.00   10.00    --   18.52  57.00-120.00   90
  6  \w    -54.00  44.00   1.00   10.00    --   18.52 -38.00 120.00   98
  7  \w     -3.00  87.00   1.00   10.00    --   18.52  57.00 150.00   90
  8  \w     -3.00  87.00   1.00   10.00    --   18.52  57.00 -60.00   90
  9  \w    -25.00  60.00   1.00   10.00    --   18.52 -99.00   0.00   85
 10  \w    -80.00 -22.00   1.00   10.00    --  -18.52 131.00 -16.65   58
 11  \w    -25.00  23.00   1.00   10.00    --  -18.52 -99.00 -30.00   48
 12  \w    -54.00  91.00   1.00   10.00    --   18.52   0.00-180.00  145
 13  \w     -1.00  78.00   1.00   10.00    --   18.52-128.00 -57.13   79
 14  \w     34.00  95.00   1.00   10.00    --   18.52 179.00 150.00   61
 15  \w    -54.00  91.00   1.00   10.00    --   18.52   0.00-150.00  145
 16  \w    -25.00  60.00   1.00   10.00    --   18.52 -99.00  90.00   85
 17  \w    -54.00  91.00   1.00   10.00    --   18.52   0.00 -90.00  145
 18  \w    -54.00  91.00   1.00   10.00    --   18.52   0.00 -60.00  145
 19  \w    -54.00  91.00   1.00   10.00    --   18.52   0.00 -30.00  145
 20  \w    -54.00  83.00   1.00   10.00    --   18.52   0.00   0.00  137
 21  \w    -54.00  91.00   1.00   10.00    --   18.52   0.00-120.00  145
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0741997000
_diffrn_orient_matrix_UB_12      -0.0167191000
_diffrn_orient_matrix_UB_13      0.0088578000
_diffrn_orient_matrix_UB_21      -0.0409402000
_diffrn_orient_matrix_UB_22      0.0627795000
_diffrn_orient_matrix_UB_23      -0.0219931000
_diffrn_orient_matrix_UB_31      0.0242127000
_diffrn_orient_matrix_UB_32      -0.0197853000
_diffrn_orient_matrix_UB_33      -0.0449299000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0560
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.898
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            40698
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.898
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.268
_diffrn_reflns_theta_min         2.531
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.284
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84425
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_description       block
_exptl_crystal_F_000             532
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.388
_refine_diff_density_min         -0.385
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     334
_refine_ls_number_reflns         6349
_refine_ls_number_restraints     20
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1113
_refine_ls_R_factor_gt           0.0747
_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^)+(0.1142P)^2^+0.4909P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1993
_refine_ls_wR_factor_ref         0.2285
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4128
_reflns_number_total             6349
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00175_si_002.cif
_cod_data_source_block           6a
_cod_original_cell_volume        1297.89(9)
_cod_database_code               4038015
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 O4 H20 N1'
_chemical_oxdiff_usercomment     'XC da DCM/C6'
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.883
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Restrained distances
 Cl2B-C28B \\sim Cl2A-C28A \\sim Cl1A-C28A \\sim Cl1B-C28B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Cl1A) = Uanis(Cl1B)
Uanis(C28A) = Uanis(C28B)
4. Rigid body (RIGU) restrains
 C28A, Cl1A, Cl2A, C28B, Cl1B, Cl2B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(Cl1B)=Sof(Cl2B)=Sof(C28B)=Sof(H28A)=Sof(H28B)=1-FVAR(1)
 Sof(C28A)=Sof(H28C)=Sof(H28D)=Sof(Cl1A)=Sof(Cl2A)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C28B(H28A,H28B), C28A(H28C,H28D)
6.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C19(H19), C12(H12), C15(H15), C23(H23), C17(H17), C27(H27),
 C11(H11), C10(H10), C9(H9), C24(H24), C25(H25), C26(H26)
6.c X=CH2 refined with riding coordinates:
 C4(H4A,H4B)
6.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              73840
_shelx_hkl_checksum              33515
_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 1.651
_oxdiff_exptl_absorpt_empirical_full_min 0.656