Scope and Mechanism of the Redox-Active 1,2-Benzoquinone Enabled Ruthenium-Catalyzed Deaminative α-Alkylation of Ketones with Amines
Kirinde Arachchige, Pandula T.; Handunneththige, Suhashini; Talipov, Marat R.; Kalutharage, Nishantha; Yi, Chae S.; ACS Catalysis 11 (2021) 13962–13972; doi:10.1021/acscatal.1c04732

data_4519179
_publ_section_title
;
 Scope and Mechanism of the Redox-Active 1,2-Benzoquinone Enabled
 Ruthenium-Catalyzed Deaminative \a-Alkylation of Ketones with Amines
;
_journal_issue                   22
_journal_name_full               'ACS Catalysis'
_journal_page_first              13962
_journal_page_last               13972
_journal_paper_doi               10.1021/acscatal.1c04732
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C20 H23 N O3'
_chemical_formula_sum            'C20 H23 N O3'
_chemical_formula_weight         325.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.866(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.16080(10)
_cell_length_b                   12.7726(4)
_cell_length_c                   25.3964(7)
_cell_measurement_reflns_used    6739
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      29.2950
_cell_measurement_theta_min      4.2670
_cell_volume                     1670.24(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3756
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.914
_diffrn_measured_fraction_theta_max 0.914
_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    -14.00  85.00   1.00    9.63    --   10.69  37.00   0.00   99
  2  \w    -20.00  30.00   1.00    9.63    --  -10.77 -99.00 -30.00   50
  3  \w    -52.00  69.00   1.00    9.63    --  -10.77  19.00 -60.00  121
  4  \w    -20.00  25.00   1.00    9.63    --   10.69 -99.00-180.00   45
  5  \w    -35.00  64.00   1.00    9.63    --  -10.77  37.00  60.00   99
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0754337000
_diffrn_orient_matrix_UB_12      -0.0348585000
_diffrn_orient_matrix_UB_13      0.0144197000
_diffrn_orient_matrix_UB_21      -0.0595242000
_diffrn_orient_matrix_UB_22      0.0432422000
_diffrn_orient_matrix_UB_23      0.0118916000
_diffrn_orient_matrix_UB_31      -0.0986746000
_diffrn_orient_matrix_UB_32      0.0005424000
_diffrn_orient_matrix_UB_33      -0.0208365000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0321
_diffrn_reflns_av_unetI/netI     0.0337
_diffrn_reflns_Laue_measured_fraction_full 0.914
_diffrn_reflns_Laue_measured_fraction_max 0.914
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            19263
_diffrn_reflns_point_group_measured_fraction_full 0.914
_diffrn_reflns_point_group_measured_fraction_max 0.914
_diffrn_reflns_theta_full        29.724
_diffrn_reflns_theta_max         29.724
_diffrn_reflns_theta_min         3.290
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.087
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.697
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.294
_exptl_crystal_description       needle
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.803
_exptl_crystal_size_mid          0.238
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.350
_refine_diff_density_min         -0.326
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     230
_refine_ls_number_reflns         4342
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0746
_refine_ls_R_factor_gt           0.0513
_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^)+(0.0449P)^2^+1.1276P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1156
_refine_ls_wR_factor_ref         0.1295
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3272
_reflns_number_total             4342
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04732_si_003.cif
_cod_data_source_block           yi4t
_cod_database_code               4519179
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C20 H23 N O3'
_reflns_odcompleteness_completeness 99.72
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{C19, C19A}
3. Uiso/Uaniso restraints and constraints
Uanis(C20) = Uanis(C20A)
Uanis(O3) = Uanis(O3A)
Uanis(C18B) = Uanis(C18A)
Uanis(C19) = Uanis(C19A)
4. Others
 Sof(C20A)=Sof(H20C)=Sof(H20D)=1-FVAR(1)
 Sof(C20)=Sof(H20A)=Sof(H20B)=FVAR(1)
 Sof(H17C)=Sof(H17D)=Sof(C18B)=Sof(H18C)=Sof(H18D)=1-FVAR(2)
 Sof(H17A)=Sof(H17B)=Sof(C18A)=Sof(H18A)=Sof(H18B)=FVAR(2)
 Sof(O3A)=1-FVAR(3)
 Sof(O3)=FVAR(3)
 Fixed Sof: C19(0.7) H19A(0.7) H19B(0.7) C19A(0.3) H19C(0.3) H19D(0.3)
5.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C17(H17C,H17D), C17(H17A,H17B), C18A(H18A,H18B),
 C18B(H18C,H18D), C19(H19A,H19B), C19A(H19C,H19D), C20(H20A,H20B), C20A(H20C,
 H20D)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C11(H11), C12(H12), C14(H14), C15(H15)
5.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_olex2_date_sample_data_collection 2019-07-24
_olex2_date_sample_submission    2019-07-23
_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 1.126
_oxdiff_exptl_absorpt_empirical_full_min 0.919