Enantioselective Three-Step Synthesis of Homo-β-proline: A Donor-Acceptor Cyclopropane as Key Intermediate.
Pilsl, Ludwig K. A.; Ertl, Thomas; Reiser, Oliver; Organic letters 19 (2017) 2754–2757; doi:10.1021/acs.orglett.7b01111

data_1546006
_publ_section_title
;
 Enantioselective Three-Step Synthesis of Homo-\b-proline: A
 Donor-Acceptor Cyclopropane as Key Intermediate.
;
_journal_issue                   10
_journal_name_full               'Organic letters'
_journal_page_first              2754
_journal_page_last               2757
_journal_paper_doi               10.1021/acs.orglett.7b01111
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H27 N O4'
_chemical_formula_sum            'C15 H27 N O4'
_chemical_formula_weight         285.37
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2bc 2'
_space_group_name_H-M_alt        'P 2 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-12-15
_audit_creation_method
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Olex2 1.2-alpha
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_cell_length_b                   8.52370(17)
_cell_length_c                   15.8573(3)
_cell_measurement_reflns_used    2490
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      70.1740
_cell_measurement_theta_min      5.5580
_cell_volume                     814.62(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.12a (release 12-09-2013 CrysAlis171 .NET)
(compiled Sep 12 2013,13:51:24)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.12a (release 12-09-2013 CrysAlis171 .NET)
(compiled Sep 12 2013,13:51:24)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.12a (release 12-09-2013 CrysAlis171 .NET)
(compiled Sep 12 2013,13:51:24)
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_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      123.00(10)
_diffrn_detector_area_resol_mean 10.3546
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
  1 omega -108.00   23.00   0.5000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.2064    0.0000  -30.0000 262

  2 omega   24.00   65.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      100.5179  -30.0000  -60.0000 82

  3 omega   67.00  132.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      100.5179   77.0000   30.0000 130

  4 omega   70.00  151.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      100.5179   61.0000 -180.0000 162

  5 omega   35.00   68.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      100.5179  -45.0000   30.0000 66

  6 omega   28.00  115.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      100.5179 -125.0000  -90.0000 174

  7 omega   24.00   51.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      100.5179  -30.0000    0.0000 54

  8 omega -115.00  -12.00   0.5000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.2064  -57.0000  -90.0000 206

  9 omega -115.00  -12.00   0.5000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.2064  -57.0000  150.0000 206

 10 omega  -69.00   -5.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   30.0000 -150.0000 128

 11 omega   73.00  121.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      100.5179   45.0000  -90.0000 96

 12 omega   23.00   69.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      100.5179  -30.0000 -120.0000 92
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_diffrn_orient_matrix_UB_11      -0.0659414000
_diffrn_orient_matrix_UB_12      -0.0252931000
_diffrn_orient_matrix_UB_13      0.0928180000
_diffrn_orient_matrix_UB_21      -0.1738245000
_diffrn_orient_matrix_UB_22      -0.1222084000
_diffrn_orient_matrix_UB_23      -0.0276135000
_diffrn_orient_matrix_UB_31      0.1754655000
_diffrn_orient_matrix_UB_32      -0.1307409000
_diffrn_orient_matrix_UB_33      0.0076627000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0498
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            4025
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.254
_diffrn_reflns_theta_min         5.580
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.676
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60468
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.12a (release 12-09-2013 CrysAlis171 .NET)
(compiled Sep 12 2013,13:51:24)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
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_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.163
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_exptl_crystal_F_000             312
_exptl_crystal_size_max          0.1519
_exptl_crystal_size_mid          0.1343
_exptl_crystal_size_min          0.0933
_refine_diff_density_max         0.100
_refine_diff_density_min         -0.129
_refine_diff_density_rms         0.027
_refine_ls_abs_structure_details
;
 Flack x determined using 525 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.11(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     187
_refine_ls_number_reflns         1515
_refine_ls_number_restraints     63
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0308
_refine_ls_R_factor_gt           0.0289
_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^)+(0.0465P)^2^+0.0109P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0757
_refine_ls_wR_factor_ref         0.0767
_reflns_Friedel_coverage         0.636
_reflns_Friedel_fraction_full    0.975
_reflns_Friedel_fraction_max     0.944
_reflns_number_gt                1422
_reflns_number_total             1515
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b01111_si_004.cif
_cod_data_source_block           mb_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 1546004--1546006.cif.'
_cod_database_code               1546006
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C15 H27 N1 O4'
_cell_oxdiff_angle_alpha         90.080(4)
_cell_oxdiff_angle_beta          90.054(4)
_cell_oxdiff_angle_gamma         89.962(4)
_cell_oxdiff_length_a            6.0263(3)
_cell_oxdiff_length_b            8.5235(5)
_cell_oxdiff_length_c            15.8594(7)
_cell_oxdiff_measurement_reflns_used 2421
_cell_oxdiff_twin_number         2
_cell_oxdiff_volume              814.62(7)
_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
2. Restrained distances
 C8-C11 \\sim C8-C10 \\sim C9-C8 \\sim C16-C13 \\sim C14-C13 \\sim C15-C13
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
C14 \\sim C16 \\sim C15 \\sim C9 \\sim C11 \\sim C10 \\sim C8 \\sim C13 \\sim
O3 \\sim O2: within 1.7A with sigma of 0.005 and sigma for terminal atoms of
0.005
4. Others
 Fixed Sof: O3(0.5) O4(0.5) C12(0.5) C4(0.5) H4A(0.5) H4B(0.5) C1(0.5)
 H1A(0.5) H1B(0.5) N1(0.5) C2(0.5) H2(0.5) C3(0.5) H3A(0.5) H3B(0.5) O1(0.5)
 C6(0.5) O2(0.5) C7(0.5) H7A(0.5) H7B(0.5) C10(0.5) H10A(0.5) H10B(0.5)
 H10C(0.5) C9(0.5) H9A(0.5) H9B(0.5) H9C(0.5) C8(0.5) C11(0.5) H11A(0.5)
 H11B(0.5) H11C(0.5) C15(0.5) H15A(0.5) H15B(0.5) H15C(0.5) C14(0.5) H14A(0.5)
 H14B(0.5) H14C(0.5) C13(0.5) C16(0.5) H16A(0.5) H16B(0.5) H16C(0.5)
5.a Ternary CH refined with riding coordinates:
 C2(H2)
5.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C1(H1A,H1B), C3(H3A,H3B), C7(H7A,H7B)
5.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C15(H15A,H15B,
 H15C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              28712
_shelx_hkl_checksum              34197
_olex2_diffrn_ambient_temperature_device 'CryoStream 700, Oxford Cryosystems'
_olex2_submission_special_instructions 'No special instructions were received'