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_4519180
_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         '1(C22 H29 N O)'
_chemical_formula_sum            'C22 H29 N O'
_chemical_formula_weight         323.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-09-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.6552(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.58070(12)
_cell_length_b                   11.25264(18)
_cell_length_c                   21.8958(5)
_cell_measurement_reflns_used    6107
_cell_measurement_temperature    100.00(14)
_cell_measurement_theta_max      70.3240
_cell_measurement_theta_min      4.0440
_cell_volume                     1851.13(6)
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3756
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_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   -115.00 -14.00   1.00    4.00    --  -42.58 -57.00  60.00  101
  2  \w   -115.00 -62.00   1.00    4.00    --  -42.58-143.00  12.00   53
  3  \w    -71.00  31.00   1.00    4.00    --  -42.58  57.00-150.00  102
  4  \w     65.00 124.00   1.00    4.00    --   42.58 169.00 139.00   59
  5  \w    -32.00  67.00   1.00    4.00    --   42.58 -37.00-120.00   99
  6  \w     27.00 118.00   1.00   16.00    --  100.00-125.00   0.00   91
  7  \w     94.00 173.00   1.00   16.00    --  100.00 125.00  30.00   79
  8  \w     74.00 173.00   1.00   16.00    --  100.00  45.00-120.00   99
  9  \w     74.00 173.00   1.00   16.00    --  100.00  45.00 -90.00   99
 10  \w     72.00 176.00   1.00   16.00    --  100.00  30.00  90.00  104
 11  \w     24.00 128.00   1.00   16.00    --  100.00 -30.00 -90.00  104
 12  \w     27.00 118.00   1.00   16.00    --  100.00-125.00 150.00   91
 13  \w     27.00 118.00   1.00   16.00    --  100.00-125.00 120.00   91
 14  \w     24.00 133.00   1.00   16.00    --  100.00 -77.00 -60.00  109
 15  \w     94.00 124.00   1.00   16.00    --  100.00 125.00-180.00   30
;
_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      -0.0334984000
_diffrn_orient_matrix_UB_12      0.0880205000
_diffrn_orient_matrix_UB_13      -0.0542105000
_diffrn_orient_matrix_UB_21      0.0165272000
_diffrn_orient_matrix_UB_22      -0.1023259000
_diffrn_orient_matrix_UB_23      -0.0456491000
_diffrn_orient_matrix_UB_31      -0.2015470000
_diffrn_orient_matrix_UB_32      -0.0230182000
_diffrn_orient_matrix_UB_33      -0.0043116000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0327
_diffrn_reflns_av_unetI/netI     0.0337
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            15681
_diffrn_reflns_point_group_measured_fraction_full 0.948
_diffrn_reflns_point_group_measured_fraction_max 0.948
_diffrn_reflns_theta_full        70.547
_diffrn_reflns_theta_max         70.547
_diffrn_reflns_theta_min         4.074
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.535
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.404
_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    1.161
_exptl_crystal_description       plate
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.305
_exptl_crystal_size_min          0.043
_refine_diff_density_max         0.260
_refine_diff_density_min         -0.211
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 2388 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.2(2)
_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     467
_refine_ls_number_reflns         6735
_refine_ls_number_restraints     87
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0599
_refine_ls_R_factor_gt           0.0527
_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^)+(0.0956P)^2^+0.2610P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1420
_refine_ls_wR_factor_ref         0.1509
_reflns_Friedel_coverage         0.824
_reflns_Friedel_fraction_full    0.906
_reflns_Friedel_fraction_max     0.906
_reflns_number_gt                5895
_reflns_number_total             6735
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04732_si_002.cif
_cod_data_source_block           yi4w
_cod_database_code               4519180
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C22 H29 N O'
_reflns_odcompleteness_completeness 99.80
_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, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C14A, C15, C16, C17, C18, C19, C20, C21, C15A, C16A, C17A, C18A, C19A, C20A,
 C21A, C14X, C15X, C16X, C17X, C18X, C19X, C20X, C21X, C22A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C14X, C15, C16, C17, C18, C19, C20, C21, C15A, C16A, C17A, C18A, C19A, C20A,
 C21A, C22A, C15X, C16X, C17X, C18X, C19X, C20X, C21X, C22X
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C14A) = Uanis(C14X)
Uanis(C15A) = Uanis(C15X)
Uanis(C16A) = Uanis(C16X)
Uanis(C17A) = Uanis(C17X)
Uanis(C18A) = Uanis(C18X)
Uanis(C19A) = Uanis(C19X)
Uanis(C20A) = Uanis(C20X)
Uanis(C21A) = Uanis(C21X)
Uanis(C22A) = Uanis(C22X)
4. Same fragment restrains
{C14A, C15A, C16A, C17A, C18A, C19A, C20A, C21A, C22A} sigma for 1-2: 0.02,
1-3: 0.04
as
{C14X, C15X, C16X, C17X, C18X, C19X, C20X, C21X, C22X}
5. Others
 Sof(H13C)=Sof(H13D)=Sof(C14X)=Sof(H14X)=Sof(C15X)=Sof(H15X)=Sof(C16X)=
 Sof(C17X)=Sof(H17X)=Sof(C18X)=Sof(H18C)=Sof(H18D)=Sof(C19X)=Sof(H19C)=
 Sof(H19D)=Sof(C20X)=Sof(H20C)=Sof(H20D)=Sof(C21X)=Sof(H21D)=Sof(H21E)=
 Sof(H21F)=Sof(C22X)=Sof(H22D)=Sof(H22E)=Sof(H22F)=1-FVAR(1)
 Sof(H13A)=Sof(H13B)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=
 Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(H18B)=Sof(C19A)=Sof(H19A)=
 Sof(H19B)=Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(C21A)=Sof(H21A)=Sof(H21B)=
 Sof(H21C)=Sof(C22A)=Sof(H22A)=Sof(H22B)=Sof(H22C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C14(H14), C15(H15), C17(H17), C14A(H14A), C15A(H15A), C17A(H17A), C14X(H14X),
 C15X(H15X), C17X(H17X)
6.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10C,H10D), C12(H12C,H12D), C13(H13E,H13F), C18(H18E,H18F),
 C19(H19E,H19F), C20(H20E,H20F), C9A(H9AA,H9AB), C10A(H10A,H10B), C12A(H12A,
 H12B), C13A(H13A,H13B), C13A(H13C,H13D), C18A(H18A,H18B), C19A(H19A,H19B),
 C20A(H20A,H20B), C18X(H18C,H18D), C19X(H19C,H19D), C20X(H20C,H20D)
6.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C1(H1B), C4(H4), C5(H5), C6(H6), C7(H7), N1A(H1A), C1A(H1AA),
 C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A)
6.d Idealised Me refined as rotating group:
 C21(H21G,H21H,H21I), C22(H22G,H22H,H22I), C21A(H21A,H21B,H21C), C22A(H22A,
 H22B,H22C), C21X(H21D,H21E,H21F), C22X(H22D,H22E,H22F)
;
_olex2_date_sample_data_collection 2019-09-03
_olex2_date_sample_submission    2019-08-14
_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 1.355
_oxdiff_exptl_absorpt_empirical_full_min 0.792