Enantioselective one-carbon expansion of aromatic rings by simultaneous formation and chromoselective irradiation of a transient coloured enolate
Saunthwal, Rakesh K.; Mortimer, James; Orr-Ewing, Andrew; Clayden, Jonathan; Chemical Science  (2022) –; doi:10.1039/D1SC06684F

data_1566124
_publ_section_title
;
 Enantioselective one-carbon expansion of aromatic rings by simultaneous
 formation and chromoselective irradiation of a transient coloured enolate
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC06684F
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H23 N O2'
_chemical_formula_sum            'C19 H23 N O2'
_chemical_formula_weight         297.38
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-04-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-05-12 deposited with the CCDC.	2022-01-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.4746(3)
_cell_length_b                   12.0701(4)
_cell_length_c                   30.0751(11)
_cell_measurement_reflns_used    9591
_cell_measurement_temperature    100
_cell_measurement_theta_max      68.46
_cell_measurement_theta_min      4.89
_cell_volume                     3439.4(2)
_computing_cell_refinement       'SAINT v8.39.0 (Bruker, 2018)'
_computing_data_collection       'Bruker SC-XRD Suite'
_computing_data_reduction        'SAINT v8.39.0 (Bruker, 2018)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker PHOTON III C7'
_diffrn_detector_type            CPAD
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'Bruker D8 Venture dual source kappa CPAD'
_diffrn_measurement_device_type  'Bruker D8 Venture dual source kappa CPAD'
_diffrn_measurement_method       '\f and \w-scan'
_diffrn_radiation_monochromator  'focusing mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0302
_diffrn_reflns_av_unetI/netI     0.0093
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            127528
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.552
_diffrn_reflns_theta_min         2.939
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\uS microsource'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.582
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.4336
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1595 before and 0.0546 after correction. The Ratio of minimum to maximum transmission is 0.5758. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.149
_exptl_crystal_description       needle
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.587
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.128
_refine_diff_density_min         -0.133
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
;
 Flack x determined using 2715 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     452
_refine_ls_number_reflns         6333
_refine_ls_number_restraints     105
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0268
_refine_ls_R_factor_gt           0.0266
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0355P)^2^+0.6587P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0672
_refine_ls_wR_factor_ref         0.0674
_reflns_Friedel_coverage         0.766
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                6290
_reflns_number_total             6333
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06684f2.cif
_cod_data_source_block           rs_660aa
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_database_code               1566124
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.726
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C36-C37 \\sim C36A-C37A \\sim C36-C38 \\sim C36A-C38A
 with sigma of 0.005
 C37-C38 \\sim C37A-C38A
 with sigma of 0.01
 N2-C36 \\sim N2A-C36A
 with sigma of 0.005
 C35-N2 \\sim C35-N2A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C36 \\sim C36A \\sim C37 \\sim C37A \\sim C38 \\sim C38A \\sim N2 \\sim N2A:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(C36A)=Sof(H36A)=Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(C38A)=
 Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(N2A)=Sof(H2A)=1-FVAR(1)
 Sof(C36)=Sof(H36)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38)=Sof(H38A)=
 Sof(H38B)=Sof(H38C)=Sof(N2)=Sof(H2)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C17(H17), C36(H36), C36A(H36A)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C22(H22), C23(H23), C24(H24), C26(H26), C28(H28), C29(H29), C30(H30),
  C31(H31), C32(H32), N2A(H2A)
5.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C37(H37A,H37B,H37C),
 C37A(H37D,H37E,H37F), C38(H38A,H38B,H38C), C38A(H38D,H38E,H38F)
;
_shelx_res_checksum              17346
_shelx_hkl_checksum              78510
_olex2_date_sample_data_collection 2021-04-15
_olex2_date_sample_submission    2021-04-13
_olex2_exptl_crystal_mounting_method 'Oil on glass fibre'
_olex2_submission_special_instructions 'No special instructions were received'