S1 Distinguishing the early and late Transition States and Exploring the Validity of σ→σ*#, σ#→σ* and σ→π* C=O Concepts in Diastereoselection from NBO Analysis Veejendra K. Yadav,* Archana Gupta, Rengarajan Balamurugan, Vardhineedi Sriramurthy, and Naganabonia Vijaya Kumar Department of Chemistry, Indian Institute of Technolgy, Kanpur-208 016, India e-mail: vijendra@iitk.ac.in Contents: HF/6-31G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of 1 S2 HF/6-31G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of 2 S2-S3 HF/6-31G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of 3 S3-S4 HF/6-31G*, B3LYP/6-31G* geometries of the axial TS 1-LiH S4 HF/6-31G*, B3LYP/6-31G* geometries of the axial TS 2-LiH S5 HF/6-31G*, B3LYP/6-31G* geometries of the axial TS 3-LiH S5-S6 HF/6-31G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of 4a S6-S7 HF/6-31G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of 4b S7-S8 HF/6-31G*, B3LYP/6-31G* geometries of anti-to-S TS 4a-LiH S8 HF/6-31G*, B3LYP/6-31G* geometries of syn-to-S TS 4a-LiH S9 HF/6-31G*, B3LYP/6-31G* geometries of anti-to-S TS 4b-LiH S9-S10 HF/6-31G*, B3LYP/6-31G* geometries of syn-to-S TS 4b-LiH S10 HF/6-31G*, HF/6-31+G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of 5b S11 HF/6-31G*, HF/6-31+G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of 5a S12 HF/6-31G*, B3LYP/6-31G* geometries of TS 5a-LiH S12-S13 HF/6-31G*, HF/6-31+G* geometries of TS 5a-MeLi S13 HF/6-31G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of TS 5a-LiCN S13-S14 HF/6-31G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of TS 5a-NaCN S14-S15 HF/6-31G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of axial TS 1-LiCN S15-S16 HF/6-31G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of axial TS 2-LiCN S16-S17 HF/6-31G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of axial TS 3-LiCN S17-S18 HF/6-31G* geometry of cyclohexanone 6 S18 HF/6-31G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of axial TS 6-LiH S19 HF/6-31G*, B3LYP/6-31G*, B3LYP/6-31+G* geometries of axial TS 6-LiCN S20 HF/6-31G* geometry of 7a S21 HF/6-31G* geometry of the TS 7a-LiCN (σ# anti σ C-H ) S21 HF/6-31G* geometry of 7b S21 HF/6-31G* geometry of the TS 7b-LiCN (σ# anti σ C-H ) S21 HF/6-31G* geometry of the TS 7b-LiCN (σ# anti σ C-C ) S22 HF/6-31G* geometry of the TS 7-LiCN (σ# anti σ C-F ) S22 HF/6-31G* geometry of 2-ax-F-cyclohexanone 8 S22 HF/6-31G*, HF/6-31+G*, B3LYP/6-31G* geometries of axial TS 8-LiCN S23 HF/6-31G*, HF/6-31+G*, B3LYP/6-31G* geometries of equatorial TS 8-LiCN S24-S25 HF/6-31G* geometry of 2-ax-F-1-ax-CN-1-eq-OLi-cyclohexane S25 HF/6-31G* geometry of 2-ax-F-1-eq-CN-1-ax-OLi-cyclohexane S25 Figures 1-9 S27-S32