Chemoselective asymmetric dearomative [3 + 2] cycloaddition reactions of purines with aminocyclopropanes
Hao, Er-Jun; Fu, Dan-Dan; Wang, Dong-Chao; Zhang, Tao; Qu, Gui-Rong; Li, Gong-Xin; Lan, Yu; Guo, Hai-Ming; Organic Chemistry Frontiers 6 (2019) 863–; doi:10.1039/C9QO00039A

data_1554706
_publ_section_title
;
 Chemoselective asymmetric dearomative [3 + 2] cycloaddition reactions of
 purines with aminocyclopropanes
;
_journal_issue                   6
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              863
_journal_paper_doi               10.1039/C9QO00039A
_journal_volume                  6
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H22 Cl N5 O8'
_chemical_formula_sum            'C21 H22 Cl N5 O8'
_chemical_formula_weight         507.89
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-03-13
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.02.02 svn.r3481 for OlexSys, GUI svn.r5470)
;
_audit_update_record
;
2018-04-17 deposited with the CCDC.
2019-02-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.146(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.9456(5)
_cell_length_b                   8.8451(3)
_cell_length_c                   23.3704(7)
_cell_measurement_reflns_used    54083
_cell_measurement_temperature    293.0(10)
_cell_measurement_theta_max      72.5090
_cell_measurement_theta_min      4.2110
_cell_volume                     5262.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.0(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0528
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -31.00  53.00   1.00    1.00    --   36.36 -57.00-150.00   84
  2  \w     10.00 104.00   1.00    1.00    --   36.36  77.00  90.00   94
  3  \w    -31.00  53.00   1.00    1.00    --   36.36 -57.00 150.00   84
  4  \w      7.00 108.00   1.00    1.00    --   36.36  19.00  90.00  101
  5  \w     23.00  90.00   1.00    1.00    --   36.36-125.00 -30.00   67
  6  \w    -33.00 106.00   1.00    1.00    --   36.36   0.00  30.00  139
  7  \w     20.00 104.00   1.00    1.00    --   36.36  57.00-150.00   84
  8  \w    -31.00  53.00   1.00    1.00    --   36.36 -57.00  90.00   84
  9  \w     23.00  90.00   1.00    1.00    --   36.36-125.00   0.00   67
 10  \w     23.00  90.00   1.00    1.00    --   36.36-125.00  30.00   67
 11  \w      1.00  75.00   1.00    1.00    --   36.36 -99.00 -30.00   74
 12  \w     20.00 104.00   1.00    1.00    --   36.36  57.00 150.00   84
 13  \w     17.00 105.00   1.00    1.00    --   36.36  38.00  90.00   88
 14  \w     20.00 104.00   1.00    1.00    --   36.36  57.00 -30.00   84
 15  \w     17.00 105.00   1.00    1.00    --   36.36  38.00-120.00   88
 16  \w    -33.00  55.00   1.00    1.00    --   36.36 -38.00 150.00   88
 17  \w     10.00 104.00   1.00    1.00    --   36.36  77.00 -30.00   94
 18  \w     23.00  90.00   1.00    1.00    --   36.36-125.00 150.00   67
 19  \w     10.00 104.00   1.00    1.00    --   36.36  77.00  60.00   94
 20  \w    -33.00  55.00   1.00    1.00    --   36.36 -38.00  30.00   88
 21  \w     20.00 104.00   1.00    1.00    --   36.36  57.00 120.00   84
 22  \w      7.00 108.00   1.00    1.00    --   36.36  19.00 120.00  101
 23  \w     71.00 178.00   1.00    4.00    --  109.31  15.00 120.00  107
 24  \w     88.00 178.00   1.00    4.00    --  109.31  30.00  30.00   90
 25  \w     42.00 136.00   1.00    4.00    --  109.31 -77.00-120.00   94
 26  \w     91.00 176.00   1.00    4.00    --  109.31  61.00  30.00   85
 27  \w     92.00 178.00   1.00    4.00    --  109.31  45.00   0.00   86
 28  \w     83.00 177.00   1.00    4.00    --  109.31  77.00   0.00   94
 29  \w     92.00 178.00   1.00    4.00    --  109.31  45.00  60.00   86
 30  \w     92.00 178.00   1.00    4.00    --  109.31  45.00  30.00   86
 31  \w     71.00 178.00   1.00    4.00    --  109.31  15.00  60.00  107
 32  \w    100.00 178.00   1.00    4.00    --  109.31 111.00-120.00   78
 33  \w     83.00 177.00   1.00    4.00    --  109.31  77.00  60.00   94
 34  \w     88.00 178.00   1.00    4.00    --  109.31  30.00  60.00   90
 35  \w     91.00 176.00   1.00    4.00    --  109.31  61.00  90.00   85
 36  \w     91.00 176.00   1.00    4.00    --  109.31  61.00   0.00   85
 37  \w     42.00 136.00   1.00    4.00    --  109.31 -77.00  30.00   94
 38  \w     88.00 178.00   1.00    4.00    --  109.31  30.00  90.00   90
 39  \w     83.00 177.00   1.00    4.00    --  109.31  77.00  30.00   94
 40  \w     88.00 178.00   1.00    4.00    --  109.31  30.00 -30.00   90
 41  \w     83.00 177.00   1.00    4.00    --  109.31  77.00 -30.00   94
 42  \w    100.00 178.00   1.00    4.00    --  109.31 111.00-180.00   78
 43  \w     92.00 178.00   1.00    4.00    --  109.31  45.00 -30.00   86
 44  \w     91.00 176.00   1.00    4.00    --  109.31  61.00  60.00   85
 45  \w     88.00 178.00   1.00    4.00    --  109.31  30.00 120.00   90
 46  \w     92.00 178.00   1.00    4.00    --  109.31  45.00  90.00   86
 47  \w     91.00 176.00   1.00    4.00    --  109.31  61.00 -30.00   85
 48  \w     88.00 178.00   1.00    4.00    --  109.31  30.00   0.00   90
 49  \w     71.00 178.00   1.00    4.00    --  109.31  15.00  30.00  107
 50  \w     83.00 177.00   1.00    4.00    --  109.31  77.00 150.00   94
 51  \w    100.00 178.00   1.00    4.00    --  109.31 111.00 -30.00   78
 52  \w     23.00  90.00   1.00    1.00    --   36.36-125.00-180.00   67
 53  \w    -33.00  55.00   1.00    1.00    --   36.36 -38.00  90.00   88
 54  \w     17.00 105.00   1.00    1.00    --   36.36  38.00 -90.00   88
 55  \w     20.00 104.00   1.00    1.00    --   36.36  57.00 -90.00   84
 56  \w     10.00 104.00   1.00    1.00    --   36.36  77.00-150.00   94
 57  \w     17.00 105.00   1.00    1.00    --   36.36  38.00 120.00   88
 58  \w     23.00  90.00   1.00    1.00    --   36.36-125.00  90.00   67
 59  \w     20.00 104.00   1.00    1.00    --   36.36  57.00 -60.00   84
 60  \w      7.00 108.00   1.00    1.00    --   36.36  19.00-150.00  101
 61  \w     23.00  90.00   1.00    1.00    --   36.36-125.00 -90.00   67
 62  \w    -31.00  53.00   1.00    1.00    --   36.36 -57.00   0.00   84
 63  \w    -33.00  55.00   1.00    1.00    --   36.36 -38.00 -90.00   88
 64  \w     17.00 105.00   1.00    1.00    --   36.36  38.00 -68.00   88
 65  \w    -31.00  53.00   1.00    1.00    --   36.36 -57.00-120.00   84
 66  \w    -18.00  66.00   1.00    1.00    --   36.36 -83.00 -28.00   84
 67  \w     10.00 104.00   1.00    1.00    --   36.36  77.00-120.00   94
 68  \w      7.00 108.00   1.00    1.00    --   36.36  19.00 -90.00  101
 69  \w    -33.00  55.00   1.00    1.00    --   36.36 -38.00 120.00   88
 70  \w     10.00 104.00   1.00    1.00    --   36.36  77.00 -90.00   94
 71  \w    -31.00  53.00   1.00    1.00    --   36.36 -57.00 120.00   84
 72  \w     20.00 104.00   1.00    1.00    --   36.36  57.00-180.00   84
 73  \w     23.00  90.00   1.00    1.00    --   36.36-125.00-120.00   67
 74  \w     10.00 104.00   1.00    1.00    --   36.36  77.00  30.00   94
 75  \w     10.00 104.00   1.00    1.00    --   36.36  77.00 150.00   94
 76  \w      1.00  75.00   1.00    1.00    --   36.36 -99.00 150.00   74
 77  \w    -31.00  53.00   1.00    1.00    --   36.36 -57.00-180.00   84
 78  \w     88.00 178.00   1.00    4.00    --  109.31  30.00-150.00   90
 79  \w     39.00 116.00   1.00    4.00    --  109.31-111.00-180.00   77
 80  \w     90.00 178.00   1.00    4.00    --  109.31  38.00 -68.00   88
 81  \w     88.00 178.00   1.00    4.00    --  109.31  30.00 -90.00   90
 82  \w     88.00 178.00   1.00    4.00    --  109.31  30.00-120.00   90
 83  \w     88.00 178.00   1.00    4.00    --  109.31  30.00 150.00   90
 84  \w     91.00 176.00   1.00    4.00    --  109.31  61.00-180.00   85
 85  \w     39.00 116.00   1.00    4.00    --  109.31-111.00  30.00   77
 86  \w     91.00 176.00   1.00    4.00    --  109.31  61.00-120.00   85
 87  \w     71.00 178.00   1.00    4.00    --  109.31  15.00 -30.00  107
 88  \w     83.00 177.00   1.00    4.00    --  109.31  77.00 -60.00   94
 89  \w     91.00 176.00   1.00    4.00    --  109.31  61.00 120.00   85
 90  \w     91.00 176.00   1.00    4.00    --  109.31  61.00 -60.00   85
 91  \w     40.00 109.00   1.00    4.00    --  109.31 -95.00-150.00   69
 92  \w     83.00 177.00   1.00    4.00    --  109.31  77.00 -90.00   94
 93  \w     91.00 176.00   1.00    4.00    --  109.31  61.00-150.00   85
 94  \w     88.00 178.00   1.00    4.00    --  109.31  30.00-180.00   90
 95  \w     83.00 177.00   1.00    4.00    --  109.31  77.00-120.00   94
 96  \w     83.00 177.00   1.00    4.00    --  109.31  77.00-180.00   94
 97  \w     91.00 176.00   1.00    4.00    --  109.31  61.00 150.00   85
 98  \w     92.00 178.00   1.00    4.00    --  109.31  45.00 120.00   86
 99  \w     83.00 177.00   1.00    4.00    --  109.31  77.00-150.00   94
100  \w     40.00 109.00   1.00    4.00    --  109.31 -95.00 -30.00   69
101  \w     83.00 177.00   1.00    4.00    --  109.31  77.00 120.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0454283000
_diffrn_orient_matrix_UB_12      -0.0667024000
_diffrn_orient_matrix_UB_13      0.0255131000
_diffrn_orient_matrix_UB_21      -0.0290525000
_diffrn_orient_matrix_UB_22      -0.0460550000
_diffrn_orient_matrix_UB_23      -0.0618476000
_diffrn_orient_matrix_UB_31      0.0277883000
_diffrn_orient_matrix_UB_32      -0.1543560000
_diffrn_orient_matrix_UB_33      0.0066944000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1610
_diffrn_reflns_av_unetI/netI     0.0474
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            98174
_diffrn_reflns_point_group_measured_fraction_full 0.942
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        67.063
_diffrn_reflns_theta_max         67.063
_diffrn_reflns_theta_min         3.631
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.739
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.05273
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35c (Rigaku Oxford Diffraction, 2017)
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    1.282
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             2112
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.350
_refine_diff_density_min         -0.511
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Flack x determined using 3330 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.003(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     637
_refine_ls_number_reflns         8872
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0667
_refine_ls_R_factor_gt           0.0641
_refine_ls_shift/su_max          0.012
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1148P)^2^+4.4232P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1749
_refine_ls_wR_factor_ref         0.1781
_reflns_Friedel_coverage         0.761
_reflns_Friedel_fraction_full    0.877
_reflns_Friedel_fraction_max     0.877
_reflns_number_gt                8381
_reflns_number_total             8872
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00039a2.cif
_cod_data_source_block           fdd-20180312
_cod_database_code               1554706
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C1 Cl1 N1 O1 '
_shelx_estimated_absorpt_t_max   0.859
_shelx_estimated_absorpt_t_min   0.489
_reflns_odcompleteness_completeness 99.96
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C4(H4), C1(H1), C45(H45), C36(H36)
2.b Secondary CH2 refined with riding coordinates:
 C47(H47A,H47B), C2(H2A,H2B), C50(H50A,H50B), C16(H16A,H16B), C51(H51A,H51B),
 C15(H15A,H15B), C25(H25A,H25B), C60(H60A,H60B)
2.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C57(H57), C41(H41), C21(H21), C56(H56), C8(H8)
2.d Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C30(H30A,H30B,H30C), C65(H65A,H65B,H65C), C61(H61A,H61B,
 H61C), C69(H69A,H69B,H69C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              79234
_shelx_fab_checksum              56975
_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 8.545
_oxdiff_exptl_absorpt_empirical_full_min 0.343