Deoxygenative α-Alkylation and α-Arylation of 1,2-Dicarbonyls
Jin, Shengfei; Dang, Hang T.; Haug, Graham C.; Nguyen, Viet D.; Arman, Hadi; Larionov, Oleg V.; Chemical Science  (2020) –; doi:10.1039/D0SC03118F

data_1558466
_publ_section_title
;
 Deoxygenative \a-Alkylation and \a-Arylation of 1,2-Dicarbonyls
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC03118F
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C8.5 H8.5 N0.5 O)'
_chemical_formula_sum            'C17 H17 N O2'
_chemical_formula_weight         267.31
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-02-21
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.10.09 svn.r3662 for Rigaku Oxford Diffraction, GUI svn.r5959)
;
_audit_update_record
;
2020-03-08 deposited with the CCDC.	2020-07-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.0271(3)
_cell_length_b                   5.71750(10)
_cell_length_c                   20.8790(4)
_cell_measurement_reflns_used    10373
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.2450
_cell_measurement_theta_min      4.3730
_cell_volume                     2748.88(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.957
_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     25.00 120.00   0.50    1.00    --   46.62  73.00 -33.00  190
  2  \w     85.00 178.00   0.50    4.00    --  106.69  73.00 -33.00  186
  3  \w     45.00  71.00   0.50    4.00    --  106.69 -61.00 120.00   52
  4  \w     34.00 101.00   0.50    4.00    --  106.69 -77.00  30.00  134
  5  \w     34.00 101.00   0.50    4.00    --  106.69 -77.00 -90.00  134
  6  \w     34.00  91.00   0.50    4.00    --  106.69 -73.00-162.00  114
  7  \w     34.00  71.00   0.50    4.00    --  106.69 -61.00-120.00   74
  8  \w     41.00  71.00   0.50    4.00    --  106.69 -61.00-150.00   60
  9  \w     34.00 111.00   0.50    4.00    --  106.69-125.00-180.00  154
 10  \w     34.00  71.00   0.50    4.00    --  106.69 -61.00 -30.00   74
 11  \w    -25.00  69.00   0.50    1.00    --   46.62 -73.00-162.00  188
 12  \w    -69.00  26.00   0.50    1.00    --  -46.62  73.00 -33.00  190
 13  \w    -51.00 -16.00   0.50    4.00    --  -88.50  45.00 150.00   70
 14  \w    -91.00 -15.00   0.50    4.00    --  -88.50  73.00 -33.00  152
 15  \w    -51.00 -16.00   0.50    4.00    --  -88.50  45.00-120.00   70
 16  \w   -119.00 -24.00   0.50    1.00    --  -46.62 -73.00-162.00  190
 17  \w   -119.00 -87.00   0.50    1.00    --  -46.62-125.00   0.00   64
 18  \w   -119.00 -87.00   0.50    1.00    --  -46.62-125.00 120.00   64
 19  \w   -160.00-101.00   0.50    4.00    --  -88.50 -77.00  90.00  118
 20  \w   -160.00-100.00   0.50    4.00    --  -88.50 -94.00 -30.00  120
 21  \w   -160.00 -66.00   0.50    4.00    --  -88.50 -73.00-162.00  188
 22  \w   -160.00 -91.00   0.50    4.00    --  -88.50 -61.00 -90.00  138
 23  \w   -160.00 -91.00   0.50    4.00    --  -88.50 -61.00 -60.00  138
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0007342000
_diffrn_orient_matrix_UB_12      -0.0305535000
_diffrn_orient_matrix_UB_13      0.0732821000
_diffrn_orient_matrix_UB_21      -0.0392017000
_diffrn_orient_matrix_UB_22      -0.2173221000
_diffrn_orient_matrix_UB_23      -0.0063922000
_diffrn_orient_matrix_UB_31      0.0542387000
_diffrn_orient_matrix_UB_32      -0.1562328000
_diffrn_orient_matrix_UB_33      -0.0056102000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0477
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            25602
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.919
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.662
_diffrn_reflns_theta_min         3.839
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.675
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.787
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.63a (Rigaku Oxford Diffraction, 2019)
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    1.292
_exptl_crystal_description       plate
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.129
_exptl_crystal_size_mid          0.107
_exptl_crystal_size_min          0.048
_refine_diff_density_max         0.501
_refine_diff_density_min         -0.231
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.3(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     368
_refine_ls_number_reflns         5316
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0596
_refine_ls_R_factor_gt           0.0565
_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^)+(0.0300P)^2^+4.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1278
_refine_ls_wR_factor_ref         0.1298
_reflns_Friedel_coverage         0.867
_reflns_Friedel_fraction_full    0.968
_reflns_Friedel_fraction_max     0.879
_reflns_number_gt                5006
_reflns_number_total             5316
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03118f2.cif
_cod_data_source_block           hpd094b
_cod_database_code               1558466
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20H20N1O2
_chemical_oxdiff_usercomment     G472-14
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7(5)
 0.3(5)
2. 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, All O(H) groups
3. Restrained distances
 H1-O3
 1.9 with sigma of 0.02
4.a Ternary CH refined with riding coordinates:
 C13(H13), C30(H30)
4.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C32(H32A,H32B)
4.c Aromatic/amide H refined with riding coordinates:
 C23(H23), C26(H26), C29(H29), C6(H6), C24(H24), C7(H7), C3(H3), C20(H20),
 C9(H9), C19(H19), C12(H12), C8(H8), C2(H2), C25(H25)
4.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C34(H34A,H34B,H34C), C17(H17A,H17B,H17C), C33(H33A,H33B,
 H33C)
4.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O4(H4)
;
_olex2_exptl_crystal_mounting_method 'nylon loop'
_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 1.290
_oxdiff_exptl_absorpt_empirical_full_min 0.785