The Difluoromethyl Group as a Masked Nucleophile: A Lewis Acid/Base Approach.
Geri, Jacob B.; Wade Wolfe, Michael M.; Szymczak, Nathaniel K.; Journal of the American Chemical Society 140 (2018) 9404–9408; doi:10.1021/jacs.8b06093

data_4132764
_publ_section_title
;
 The Difluoromethyl Group as a Masked Nucleophile: A Lewis Acid/Base
 Approach.
;
_journal_issue                   30
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9404
_journal_page_last               9408
_journal_paper_doi               10.1021/jacs.8b06093
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C25 H47 B3 F2 K N3 O6'
_chemical_formula_sum            'C25 H47 B3 F2 K N3 O6'
_chemical_formula_weight         595.18
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-05-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                88.900(2)
_cell_angle_beta                 89.950(3)
_cell_angle_gamma                86.561(2)
_cell_formula_units_Z            4
_cell_length_a                   9.4486(3)
_cell_length_b                   14.7590(3)
_cell_length_c                   22.6127(9)
_cell_measurement_reflns_used    13706
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.8930
_cell_measurement_theta_min      3.5260
_cell_volume                     3147.12(17)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.973
_diffrn_measured_fraction_theta_max 0.941
_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   -110.00  70.00   1.00    1.00    --  -20.00   0.00-180.00  180
  2  \w    -45.00   0.00   1.00    1.00    --  -20.00  72.00   0.00   45
  3  \w    -45.00   0.00   1.00    1.00    --  -20.00  72.00   0.00   45
  4  \w    -25.00  43.00   1.00    1.00    --  -20.00  36.00 120.00   68
  5  \w    -45.00   0.00   1.00    1.00    --  -20.00  72.00-180.00   45
  6  \w   -173.00-128.00   1.00    5.00    --  -92.00 -36.00 120.00   45
  7  \w   -133.00 -88.00   1.00    5.00    --  -92.00 -36.00 -60.00   45
  8  \w   -104.00 -59.00   1.00    5.00    --  -92.00  36.00  60.00   45
  9  \w   -122.00 -77.00   1.00    5.00    --  -92.00 -72.00  60.00   45
 10  \w   -174.00 -78.00   1.00    5.00    --  -92.00 -72.00-120.00   96
 11  \w    -93.00 -35.00   1.00    5.00    --  -92.00  36.00-120.00   58
 12  \w   -176.00 -77.00   1.00    5.00    --  -92.00 -72.00 -60.00   99
 13  \w   -147.00 -75.00   1.00    5.00    --  -92.00 -72.00-180.00   72
 14  \w   -176.00 -77.00   1.00    5.00    --  -92.00 -72.00 120.00   99
 15  \w   -177.00-116.00   1.00    5.00    --  -92.00 -36.00  60.00   61
 16  \w    -87.00  -9.00   1.00    5.00    --  -92.00  36.00 -60.00   78
 17  \w   -102.00 -14.00   1.00    5.00    --  -92.00  36.00   0.00   88
 18  \w   -102.00 -21.00   1.00    5.00    --  -92.00  72.00 120.00   81
 19  \w   -175.00-104.00   1.00    5.00    --  -92.00 -36.00   0.00   71
 20  \w   -104.00 -52.00   1.00    5.00    --  -92.00  72.00  60.00   52
 21  \w   -109.00 -14.00   1.00    5.00    --  -92.00  72.00-120.00   95
 22  \w   -105.00 -24.00   1.00    5.00    --  -92.00  36.00-120.00   81
 23  \w   -105.00  -2.00   1.00    5.00    --  -92.00  36.00-180.00  103
 24  \w   -106.00  -2.00   1.00    5.00    --  -92.00  72.00 -60.00  104
 25  \w   -106.00  -2.00   1.00    5.00    --  -92.00  72.00 -60.00  104
 26  \w   -107.00 -29.00   1.00    5.00    --  -92.00  72.00   0.00   78
 27  \w   -117.00 -72.00   1.00    5.00    --  -92.00  72.00 180.00   45
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0639085000
_diffrn_orient_matrix_UB_12      0.0550942000
_diffrn_orient_matrix_UB_13      -0.0509060000
_diffrn_orient_matrix_UB_21      -0.0587971000
_diffrn_orient_matrix_UB_22      -0.0651101000
_diffrn_orient_matrix_UB_23      -0.0450776000
_diffrn_orient_matrix_UB_31      -0.1383460000
_diffrn_orient_matrix_UB_32      0.0605305000
_diffrn_orient_matrix_UB_33      -0.0043794000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0625
_diffrn_reflns_Laue_measured_fraction_full 0.973
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -1
_diffrn_reflns_number            11330
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.941
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.525
_diffrn_reflns_theta_min         3.000
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.925
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73198
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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    1.256
_exptl_crystal_description       block
_exptl_crystal_F_000             1272
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.906
_refine_diff_density_min         -0.758
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     849
_refine_ls_number_reflns         11330
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1165
_refine_ls_R_factor_gt           0.1049
_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^)+(0.1800P)^2^+3.8429P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2898
_refine_ls_wR_factor_ref         0.3063
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9238
_reflns_number_total             11330
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b06093_si_001.cif
_cod_data_source_block           jg4167_tw
_cod_original_cell_volume        3147.14(16)
_cod_database_code               4132764
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C25H47B3F2KN3O6
_shelx_estimated_absorpt_t_max   0.893
_shelx_estimated_absorpt_t_min   0.711
_reflns_odcompleteness_completeness 94.49
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     70.42
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.716(6)
 0.284(6)
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
3. Restrained distances
 C32-B63 \\sim C103-B65 \\sim C103-B65A
 with sigma of 0.01
4. Same fragment restrains
{B63, C71, N1, C72, B61, C73, N3, C74, B64, C75, N2, C76} sigma for 1-2: 0.02,
1-3: 0.04
as
{B65, C101, N4, C102, B67, C112, N5, C113, B66, C111, N6, C110}
{B63, C71, N1, C72, B61, C73, N3, C74, B64, C75, N2, C76} sigma for 1-2: 0.02,
1-3: 0.04
as
{B65A, C1, N4A, C2, B67A, C3, N5A, C4, B66A, C5, N6A, C6}
5. Others
 Sof(B65A)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(N4A)=Sof(C2)=Sof(H2A)=
 Sof(H2B)=Sof(H2C)=Sof(B67A)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(N5A)=
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(B66A)=Sof(C5)=Sof(H5A)=Sof(H5B)=
 Sof(H5C)=Sof(N6A)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=1-FVAR(1)
 Sof(B65)=Sof(C101)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(N4)=Sof(C102)=Sof(H10D)=
 Sof(H10E)=Sof(H10F)=Sof(B67)=Sof(C112)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(N5)=
 Sof(C113)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(B66)=Sof(C111)=Sof(H11G)=Sof(H11H)=
 Sof(H11I)=Sof(N6)=Sof(C110)=Sof(H11J)=Sof(H11K)=Sof(H11L)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C94(H94A,H94B), C96(H96A,H96B), C100(H10G,H10H), C93(H93A,H93B), C90(H90A,
 H90B), C89(H89A,H89B), C99(H99A,H99B), C91(H91A,H91B), C85(H85A,H85B),
 C92(H92A,H92B), C80(H80A,H80B), C82(H82A,H82B), C86(H86A,H86B), C97(H97A,H97B),
  C88(H88A,H88B), C83(H83A,H83B), C95(H95A,H95B), C98(H98A,H98B), C79(H79A,
 H79B), C81(H81A,H81B), C84(H84A,H84B), C87(H87A,H87B), C77(H77A,H77B),
 C78(H78A,H78B)
6.b Aromatic/amide H refined with riding coordinates:
 C109(H109), C27(H27), C31(H31), C105(H105), C106(H106), C41(H41), C108(H108),
 C56(H56), C107(H107), C70(H70)
6.c Idealised Me refined as rotating group:
 C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C74(H74A,H74B,
 H74C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C101(H10A,H10B,H10C),
 C102(H10D,H10E,H10F), C112(H11A,H11B,H11C), C113(H11D,H11E,H11F), C111(H11G,
 H11H,H11I), C110(H11J,H11K,H11L), C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,
 H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.364
_oxdiff_exptl_absorpt_empirical_full_min 0.628