Sustainable synthesis of enantiopure fluorolactam derivatives by a selective direct fluorination – amidase strategy
Willis, Nicky J.; Fisher, Craig A.; Alder, Catherine M.; Harsanyi, Antal; Shukla, Lena; Adams, Joseph P.; Sandford, Graham; Green Chem. 18 (2016) 1313–; doi:10.1039/C5GC02209F

data_7222918
_publ_section_title
;
 Sustainable synthesis of enantiopure fluorolactam derivatives by a
 selective direct fluorination -- amidase strategy
;
_journal_issue                   5
_journal_name_full               'Green Chem.'
_journal_page_first              1313
_journal_paper_doi               10.1039/C5GC02209F
_journal_volume                  18
_journal_year                    2016
_chemical_formula_moiety         'Cl, C8 H15 F N O4'
_chemical_formula_sum            'C8 H15 Cl F N O4'
_chemical_formula_weight         243.66
_chemical_name_systematic
;
 dimethyl (2-aminopropyl)fluoromalonate hydrochloride 
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-03-13
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-05-20 deposited with the CCDC.
2015-10-13 downloaded from the CCDC.
;
_cell_angle_alpha                100.738(7)
_cell_angle_beta                 96.625(6)
_cell_angle_gamma                94.612(6)
_cell_formula_units_Z            2
_cell_length_a                   5.8210(4)
_cell_length_b                   6.4875(5)
_cell_length_c                   15.7485(12)
_cell_measurement_reflns_used    3123
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      32.2490
_cell_measurement_theta_min      3.2000
_cell_volume                     577.23(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      120.0
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 16.1511
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -37.00   37.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       28.9587  -57.0000  120.0000 74

  2 omega   -1.00   75.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       28.9587 -112.0000   83.0000 76

  3 omega   -1.00   98.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       28.9587   77.0000  -30.0000 99

  4 omega  -19.00    7.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       28.9587 -100.0000 -150.0000 26

  5 omega   21.00   71.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       28.9587 -100.0000 -150.0000 50

  6 omega  -12.00  102.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       28.9587   19.0000  -60.0000 114

  7 omega -104.00  -35.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -      -28.3337 -178.0000 -150.0000 69

  8 omega  -97.00   -7.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -      -28.3337  -57.0000   30.0000 90

  9 omega   -1.00   38.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       28.9587   77.0000 -150.0000 39

 10 omega    3.00  101.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       28.9587   38.0000  150.0000 98
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       \w-scan
_diffrn_orient_matrix_UB_11      0.0842586000
_diffrn_orient_matrix_UB_12      0.0045224000
_diffrn_orient_matrix_UB_13      -0.0289226000
_diffrn_orient_matrix_UB_21      0.0897726000
_diffrn_orient_matrix_UB_22      0.0025254000
_diffrn_orient_matrix_UB_23      0.0348143000
_diffrn_orient_matrix_UB_31      -0.0074563000
_diffrn_orient_matrix_UB_32      -0.1117729000
_diffrn_orient_matrix_UB_33      -0.0095307000
_diffrn_radiation_collimation    monochromator
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0419
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            8623
_diffrn_reflns_theta_full        28.00
_diffrn_reflns_theta_max         28.00
_diffrn_reflns_theta_min         2.66
_diffrn_source                   'Enhance (Mo) X-ray Source'
_diffrn_source_type              'sealed tube'
_exptl_absorpt_coefficient_mu    0.340
_exptl_absorpt_correction_T_max  0.984
_exptl_absorpt_correction_T_min  0.900
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.402
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             256
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.556
_refine_diff_density_min         -0.273
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.165
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     139
_refine_ls_number_reflns         2785
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.165
_refine_ls_R_factor_all          0.0626
_refine_ls_R_factor_gt           0.0521
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0350P)^2^+0.8000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1240
_refine_ls_wR_factor_ref         0.1289
_reflns_number_gt                2374
_reflns_number_total             2785
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c5gc02209f6.cif
_cod_data_source_block           4c_15srv065
_cod_depositor_comments
'Adding full bibliography for 7222916--7222921.cif.'
_cod_original_cell_volume        577.23(7)
_cod_database_code               7222918
_chemical_oxdiff_formula         'C8 H15 Cl1 F1 N1 O4'
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.44
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1D,H1E), C2(H2A,H2B), C3(H3A,H3B)
2.b Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C)
;