Synthesis of Enantioenriched Fluorinated Enol Silanes Enabled by Asymmetric Reductive Coupling of Fluoroalkylacylsilanes and 1,3-Enynes and Brook Rearrangement
Fang, Xiaowu; Wen, Songwei; Jin, Peishen; Bao, Wenjing; Liu, Shanshan; Cong, Hengjiang; Shen, Xiao; ACS Catalysis  (2022) 2150–2157; doi:10.1021/acscatal.2c00100

data_4519288
_publ_section_title
;
 Synthesis of Enantioenriched Fluorinated Enol Silanes Enabled by
 Asymmetric Reductive Coupling of Fluoroalkylacylsilanes and 1,3-Enynes
 and Brook Rearrangement
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              2150
_journal_page_last               2157
_journal_paper_doi               10.1021/acscatal.2c00100
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H21 F2 N O3 Si'
_chemical_formula_sum            'C20 H21 F2 N O3 Si'
_chemical_formula_weight         389.47
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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             2019-12-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                97.232(4)
_cell_angle_beta                 97.041(5)
_cell_angle_gamma                109.612(6)
_cell_formula_units_Z            4
_cell_length_a                   9.1912(7)
_cell_length_b                   12.9247(8)
_cell_length_c                   18.6126(5)
_cell_measurement_reflns_used    6505
_cell_measurement_temperature    274(30)
_cell_measurement_theta_max      57.9010
_cell_measurement_theta_min      3.6310
_cell_volume                     2033.8(2)
_computing_cell_refinement
'CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)'
_computing_data_collection
'CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)'
_computing_data_reduction
'CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 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      air
_diffrn_ambient_temperature      274(30)
_diffrn_detector                 'Hybrid Pixel Counting (HPC) detector'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku HyPix-6000HE'
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.989
_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    -84.00  42.00   0.50    2.33    --    5.00 -38.00 120.00  252
  2  \w   -136.00 -13.00   0.50    2.33    --  -46.70 -57.00  60.00  246
  3  \w    -80.00  43.00   0.50    2.33    --  -46.70  57.00 -60.00  246
  4  \w   -136.00  -8.00   0.50    2.33    --  -46.70 -76.00 -30.00  256
  5  \w   -136.00  -8.00   0.50    2.33    --  -46.70 -76.00 120.00  256
  6  \w   -136.00  -8.00   0.50    2.33    --  -46.70 -76.00-120.00  256
  7  \w   -153.00 -26.00   0.50    2.33    --  -64.00 -75.00-146.78  254
  8  \w   -157.00 -30.00   0.50    2.33    --  -68.00 -76.00  84.65  254
  9  \w   -161.00 -34.00   0.50    2.33    --  -72.00 -74.00 -15.57  254
 10  \w   -161.00 -34.00   0.50    2.33    --  -72.00 -76.00 131.97  254
 11  \w   -165.00 -38.00   0.50    9.33    --  -76.00 -76.00  67.89  254
 12  \w   -165.00 -38.00   0.50    9.33    --  -76.00 -74.00 -43.44  254
 13  \w   -165.00 -38.00   0.50    9.33    --  -76.00 -76.00 -61.66  254
 14  \w   -165.00 -39.00   0.50    9.33    --  -76.00 -73.00-165.74  252
 15  \w   -165.00 -38.00   0.50    9.33    --  -76.00 -75.00 160.01  254
 16  \w   -169.00 -42.00   0.50    9.33    --  -80.00 -76.00 108.76  254
 17  \w   -169.00 -42.00   0.50    9.33    --  -80.00 -75.00  41.05  254
 18  \w   -177.00 -53.00   0.50    9.33    --  -88.00 -66.00  79.87  248
 19  \w   -177.00 -54.00   0.50    9.33    --  -88.00 -62.00 156.11  246
 20  \w   -177.00 -51.00   0.50    9.33    --  -88.00 -73.00 172.70  252
 21  \w   -177.00 -54.00   0.50    9.33    --  -88.00 -65.00  98.90  246
 22  \w   -177.00 -52.00   0.50    9.33    --  -88.00 -70.00 -55.19  250
 23  \w   -177.00 -51.00   0.50    9.33    --  -88.00 -72.00 -78.99  252
 24  \w   -177.00 -51.00   0.50    9.33    --  -88.00 -72.00-101.58  252
 25  \w   -177.00 -52.00   0.50    9.33    --  -88.00 -70.00  19.62  250
 26  \w   -177.00 -51.00   0.50    9.33    --  -88.00 -72.00-101.58  252
 27  \w   -181.00 -54.00   0.50    9.33    --  -92.00 -75.00 -21.11  254
 28  \w   -181.00 -58.00   0.50    9.33    --  -92.00 -63.00-132.19  246
 29  \w   -181.00 -54.00   0.50    9.33    --  -92.00 -75.00 148.18  254
 30  \w   -181.00 -54.00   0.50    9.33    --  -92.00 -76.00-145.79  254
 31  \w   -136.00  -8.00   0.50    9.33    --  -97.30  76.00 -30.00  256
 32  \w   -187.00 -64.00   0.50    9.33    --  -97.30 -57.00  60.00  246
 33  \w   -136.00  -8.00   0.50    9.33    --  -97.30  76.00 150.00  256
 34  \w   -186.00 -59.00   0.50    9.33    --  -97.30 -76.00   0.00  254
 35  \w    -94.00 -40.00   0.50    9.33    --  -97.30  76.00-150.00  108
 36  \w    -76.00 -24.00   0.50    9.33    --  -97.30  76.00 -90.00  104
 37  \w   -133.00 -82.00   0.50    9.33    --  -97.30  76.00 -90.00  102
 38  \w   -128.00-101.00   0.50    9.33    --  -97.30  76.00-150.00   54
 39  \w    -36.00  -8.00   0.50    9.33    --  -97.30  76.00  60.00   56
 40  \w   -135.00 -42.00   0.50    9.33    --  -97.30  76.00  60.00  186
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       'profile data from \w-scans and \phi-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1800136000
_diffrn_orient_matrix_UB_12      0.0490773000
_diffrn_orient_matrix_UB_13      0.0080018000
_diffrn_orient_matrix_UB_21      0.0159978000
_diffrn_orient_matrix_UB_22      -0.0037842000
_diffrn_orient_matrix_UB_23      0.0829055000
_diffrn_orient_matrix_UB_31      0.0040767000
_diffrn_orient_matrix_UB_32      -0.1188124000
_diffrn_orient_matrix_UB_33      -0.0157267000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  'VariMax VHF'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.3016
_diffrn_reflns_av_unetI/netI     0.1546
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            54460
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        64.998
_diffrn_reflns_theta_max         64.998
_diffrn_reflns_theta_min         2.431
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           30.0
_diffrn_source_power             1.2
_diffrn_source_target            Cu
_diffrn_source_type              'Rigaku MicroMax-007HF'
_diffrn_source_voltage           40.0
_exptl_absorpt_coefficient_mu    1.350
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48643
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.272
_exptl_crystal_description       plate
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.506
_refine_diff_density_min         -0.402
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.05(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.138
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     894
_refine_ls_number_reflns         13203
_refine_ls_number_restraints     675
_refine_ls_restrained_S_all      1.117
_refine_ls_R_factor_all          0.2528
_refine_ls_R_factor_gt           0.1285
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3256
_refine_ls_wR_factor_ref         0.4322
_reflns_Friedel_coverage         1.000
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                5193
_reflns_number_total             13203
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs2c00100_si_002.cif
_cod_data_source_block           wensongwei-wsw-4-74-250k-191223
_cod_database_code               4519288
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C78 H90 F3 N7 O16 Si4 '
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.948
_reflns_odcompleteness_completeness 98.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.05(11)
 -0.05(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
3. Uiso/Uaniso restraints and constraints
C68 \\sim C67 \\sim C66 \\sim C65 \\sim C64 \\sim C63 \\sim C62 \\sim C61:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C4 \\sim C3 \\sim C2 \\sim C1 \\sim C6 \\sim C5: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
F7 \\sim C72 \\sim F8: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C49(H49), C69(H69), C52(H52), C29(H29), C32(H32), C12(H12), C9(H9), C72(H72)
4.b Aromatic/amide H refined with riding coordinates:
 C46(H46), C45(H45), C43(H43), C42(H42), C79(H79), C80(H80), C76(H76),
 C77(H77), C78(H78), C3(H3A), C2(H2), C6(H6), C5(H5), C22(H22), C23(H23),
 C25(H25), C26(H26), C40(H40), C39(H39), C38(H38), C37(H37), C36(H36), C20(H20),
  C19(H19), C18(H18), C17(H17), C16(H16), C66(H66), C65(H65), C63(H63),
 C62(H62), C56(H56), C57(H57), C58(H58), C59(H59), C60(H60)
4.c Fitted hexagon refined as free rotating group:
 C41(C46,C45,C44,C43,C42), C79(C80,C75,C76,C77,C78), C4(C3,C2,C1,C6,C5),
 C21(C22,C23,C24,C25,C26), C35(C40,C39,C38,C37,C36), C15(C20,C19,C18,C17,C16),
 C66(C65,C64,C63,C62,C61), C55(C56,C57,C58,C59,C60)
4.d Idealised Me refined as rotating group:
 C73(H73A,H73B,H73C), C30(H30A,H30B,H30C), C54(H54A,H54B,H54C), C33(H33A,H33B,
 H33C), C34(H34A,H34B,H34C), C10(H10A,H10B,H10C), C50(H50A,H50B,H50C), C53(H53A,
 H53B,H53C), C70(H70A,H70B,H70C), C14(H14A,H14B,H14C), C13(H13A,H13B,H13C),
 C74(H74A,H74B,H74C)
4.e Idealised tetrahedral OH refined as rotating group:
 O3(H3), O6(H6A), O9(H9A), O12(H12A)
;
_shelx_res_checksum              7687
_shelx_hkl_checksum              92702
_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 5.280
_oxdiff_exptl_absorpt_empirical_full_min 0.168