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_1558464
_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_formula_moiety         'C16 H14 F O2'
_chemical_formula_sum            'C16 H14 F O2'
_chemical_formula_weight         257.27
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2020-01-29
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.10.09 svn.r3662 for Rigaku Oxford Diffraction, GUI svn.r5959)
;
_audit_update_record
;
2020-03-07 deposited with the CCDC.	2020-07-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.690(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.64360(10)
_cell_length_b                   36.3180(5)
_cell_length_c                   6.67680(10)
_cell_measurement_reflns_used    8607
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.0710
_cell_measurement_theta_min      2.4210
_cell_volume                     1303.79(4)
_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    'ShelXS n/a (Sheldrick, 2008)'
_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 0.997
_diffrn_measured_fraction_theta_max 0.966
_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    -81.00   3.00   0.50    0.05    --  -46.87 105.00 168.00  168
  2  \w     18.00  85.00   0.50    0.05    --   46.87-105.00  68.00  134
  3  \w    -81.00 -15.00   0.50    0.21    --  -88.50 105.00 168.00  132
  4  \w   -160.00 -83.00   0.50    0.21    --  -88.50-105.00  68.00  154
  5  \w    105.00 178.00   0.50    0.21    --  106.69 105.00 168.00  146
  6  \w     34.00 106.00   0.50    0.21    --  106.69-105.00  68.00  144
  7  \w   -120.00 -87.00   0.50    0.05    --  -46.87-125.00-150.00   66
  8  \w   -120.00 -83.00   0.50    0.05    --  -46.87 -57.00   0.00   74
  9  \w     83.00 120.00   0.50    0.05    --   46.87  57.00-180.00   74
 10  \w     83.00 120.00   0.50    0.05    --   46.87  57.00 150.00   74
 11  \w     83.00 120.00   0.50    0.05    --   46.87  57.00-120.00   74
 12  \w    -51.00 -16.00   0.50    0.21    --  -88.50  45.00 -30.00   70
 13  \w    -51.00 -16.00   0.50    0.21    --  -88.50  45.00 150.00   70
 14  \w    -51.00 -16.00   0.50    0.21    --  -88.50  45.00  30.00   70
 15  \w    -51.00 -16.00   0.50    0.21    --  -88.50  45.00 -60.00   70
 16  \w    -51.00 -16.00   0.50    0.21    --  -88.50  45.00   0.00   70
 17  \w    -51.00 -16.00   0.50    0.21    --  -88.50  45.00 120.00   70
 18  \w     34.00 101.00   0.50    0.21    --  106.69 -77.00  90.00  134
 19  \w     92.00 178.00   0.50    0.21    --  106.69  45.00 -30.00  172
 20  \w     34.00  71.00   0.50    0.21    --  106.69 -61.00 120.00   74
 21  \w     34.00  71.00   0.50    0.21    --  106.69 -61.00-150.00   74
 22  \w     95.00 178.00   0.50    0.21    --  106.69 125.00 -60.00  166
 23  \w     34.00  71.00   0.50    0.21    --  106.69 -61.00  90.00   74
 24  \w     34.00  71.00   0.50    0.21    --  106.69 -61.00-180.00   74
 25  \w     34.00  71.00   0.50    0.21    --  106.69 -61.00 -90.00   74
 26  \w     34.00  71.00   0.50    0.21    --  106.69 -61.00 -30.00   74
 27  \w     32.00 121.00   0.50    0.05    --   46.87  37.00 -30.00  178
 28  \w     32.00 121.00   0.50    0.05    --   46.87  37.00  90.00  178
 29  \w     83.00 120.00   0.50    0.05    --   46.87  57.00-150.00   74
 30  \w     32.00 121.00   0.50    0.05    --   46.87  37.00-180.00  178
 31  \w     83.00 120.00   0.50    0.05    --   46.87  57.00 120.00   74
 32  \w   -163.00-103.00   0.50    0.21    --  -88.50 -30.00  90.00  120
;
_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      0.2525481000
_diffrn_orient_matrix_UB_12      0.0193593000
_diffrn_orient_matrix_UB_13      0.0365939000
_diffrn_orient_matrix_UB_21      0.1125178000
_diffrn_orient_matrix_UB_22      -0.0361342000
_diffrn_orient_matrix_UB_23      -0.0510620000
_diffrn_orient_matrix_UB_31      -0.0752497000
_diffrn_orient_matrix_UB_32      0.0109162000
_diffrn_orient_matrix_UB_33      -0.2338760000
_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  0.0368
_diffrn_reflns_av_unetI/netI     0.0220
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       5
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            15026
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.520
_diffrn_reflns_theta_min         2.433
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.783
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.671
_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    1.311
_exptl_crystal_description       plate
_exptl_crystal_F_000             540
_exptl_crystal_size_max          0.145
_exptl_crystal_size_mid          0.057
_exptl_crystal_size_min          0.048
_refine_diff_density_max         0.460
_refine_diff_density_min         -0.398
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     183
_refine_ls_number_reflns         2642
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0621
_refine_ls_R_factor_gt           0.0600
_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^)+(0.0200P)^2^+2.2000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1248
_refine_ls_wR_factor_ref         0.1258
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2515
_reflns_number_total             2642
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03118f2.cif
_cod_data_source_block           hpd073a
_cod_database_code               1558464
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20H20N1O2F1
_chemical_oxdiff_usercomment     G451-5
_shelx_estimated_absorpt_t_max   0.963
_shelx_estimated_absorpt_t_min   0.895
_reflns_odcompleteness_completeness 99.96
_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, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C10A) = Uanis(C9A) = Uanis(C10B) = Uanis(C9B)
3. Others
 Fixed Sof: F1A(0.75) F1B(0.25) C10A(0.9) H10A(0.9) H10B(0.9) H10C(0.9)
 C9A(0.9) H9AA(0.9) H9AB(0.9) H7A(0.9) H7B(0.1) C9B(0.1) H9BA(0.1) H9BB(0.1)
 C10B(0.1) H10D(0.1) H10E(0.1) H10F(0.1)
4.a Riding coordinates:
 O1(H1)
4.b Ternary CH refined with riding coordinates:
 C7(H7A), C7(H7B)
4.c Secondary CH2 refined with riding coordinates:
 C9A(H9AA,H9AB), C9B(H9BA,H9BB)
4.d Aromatic/amide H refined with riding coordinates:
 C12(H12), C15(H15), C16(H16), C6(H6), C14(H14), C2(H2), C13(H13)
4.e Idealised Me refined as rotating group:
 C10A(H10A,H10B,H10C), C10B(H10D,H10E,H10F)
;
_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 1.394
_oxdiff_exptl_absorpt_empirical_full_min 0.846