Synthesis of Difluoroalkyl Unsaturated β-Amino Acid Derivatives Exclusively through Alkyne Difunctionalization.
Wang, Qiang; Jin, Jia-Ni; Chen, Xi; Wang, Xin-Gang; Zhang, Bo-Sheng; Ma, Jun-Wei; Liang, Yong-Min; The Journal of organic chemistry 83 (2018) 14626–14636; doi:10.1021/acs.joc.8b02440

data_4035695
_publ_section_title
;
 Synthesis of Difluoroalkyl Unsaturated \b-Amino Acid Derivatives
 Exclusively through Alkyne Difunctionalization.
;
_journal_issue                   23
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              14626
_journal_page_last               14636
_journal_paper_doi               10.1021/acs.joc.8b02440
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C12 H17 F2 N O5'
_chemical_formula_sum            'C12 H17 F2 N O5'
_chemical_formula_weight         293.26
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2018-03-05
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                74.167(8)
_cell_angle_beta                 81.776(9)
_cell_angle_gamma                84.811(9)
_cell_formula_units_Z            2
_cell_length_a                   5.3680(6)
_cell_length_b                   8.8589(9)
_cell_length_c                   15.7536(14)
_cell_measurement_reflns_used    1233
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.2910
_cell_measurement_theta_min      5.2030
_cell_volume                     712.28(13)
_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)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.965
_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    -17.00  80.00   1.00    1.00    --   54.00 -38.00 150.00   97
  2  \w     76.00 113.00   1.00    1.00    --  108.00-111.00 120.00   37
  3  \w    103.00 130.00   1.00    1.00    --  108.00 -91.00  60.00   27
  4  \w     63.00 129.00   1.00    1.00    --  108.00 -50.00 -60.00   66
  5  \w     66.00 116.00   1.00    1.00    --  108.00-111.00 -30.00   50
  6  \w     67.00 132.00   1.00    1.00    --  108.00 -38.00   0.00   65
  7  \w     95.00 170.00   1.00    1.00    --  108.00  63.00 -60.00   75
  8  \w    146.00 173.00   1.00    1.00    --  108.00 111.00-120.00   27
  9  \w    113.00 140.00   1.00    1.00    --  108.00 111.00-120.00   27
 10  \w     41.00 111.00   1.00    1.00    --   54.00  57.00  90.00   70
 11  \w    108.00 177.00   1.00    1.00    --  108.00 111.00 120.00   69
 12  \w     59.00 128.00   1.00    1.00    --  108.00 -50.00 120.00   69
 13  \w     52.00  85.00   1.00    1.00    --  108.00 -91.00  60.00   33
 14  \w     42.00  69.00   1.00    1.00    --  108.00 -63.00 120.00   27
 15  \w     43.00 177.00   1.00    1.00    --  108.00   0.00  90.00  134
 16  \w     59.00 109.00   1.00    1.00    --  108.00-111.00-120.00   50
 17  \w     42.00 130.00   1.00    1.00    --  108.00 -50.00-150.00   88
 18  \w     24.00 123.00   1.00    1.00    --   54.00  77.00 -60.00   99
 19  \w      6.00  65.00   1.00    1.00    --   54.00 -57.00 -30.00   59
 20  \w      1.00  54.00   1.00    1.00    --    0.00  57.00   0.00   53
 21  \w    -26.00  13.00   1.00    1.00    --    0.00 -57.00-150.00   39
 22  \w    -62.00 -35.00   1.00    1.00    --    0.00 -57.00-150.00   27
 23  \w     29.00 109.00   1.00    1.00    --   54.00-125.00 150.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0234550000
_diffrn_orient_matrix_UB_12      0.1190424000
_diffrn_orient_matrix_UB_13      0.0533786000
_diffrn_orient_matrix_UB_21      0.0522074000
_diffrn_orient_matrix_UB_22      0.1292562000
_diffrn_orient_matrix_UB_23      -0.0874150000
_diffrn_orient_matrix_UB_31      -0.2846989000
_diffrn_orient_matrix_UB_32      0.0434812000
_diffrn_orient_matrix_UB_33      0.0012758000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0236
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            4165
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.963
_diffrn_reflns_theta_min         5.254
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.061
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78078
_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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.367
_exptl_crystal_description       block
_exptl_crystal_F_000             308
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.690
_refine_diff_density_min         -0.385
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     184
_refine_ls_number_reflns         2617
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.121
_refine_ls_R_factor_all          0.0921
_refine_ls_R_factor_gt           0.0760
_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^)+(0.1569P)^2^+0.1789P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2293
_refine_ls_wR_factor_ref         0.2588
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1948
_reflns_number_total             2617
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02440_si_002.cif
_cod_data_source_block           liangym_0305
_cod_original_cell_volume        712.29(13)
_cod_database_code               4035695
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.06
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O5)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C8(H8A,H8B), C11(H11A,H11B)
3.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C5(H5)
3.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C12(H12A,H12B,H12C)
3.d Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_olex2_date_sample_data_collection 2018-03-05
_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 1.815
_oxdiff_exptl_absorpt_empirical_full_min 0.719