TABLE 7.

PPFMO analysis of disubstituted glycals and dideoxypentenosides (permethylated)^a

deoxyglycal	atom	cαb	cβb	pc	expt d
4-deoxyglucal (11)	C1	−0.182	0.169	0.005 (α)	α (>20:1)
	C2	−0.739	0.692	0.067 (α)
4-deoxyallal (3)	C1	−0.156	0.131	0.007 (β)	β (>20:1)
	C2	−0.737	0.746	0.014 (β)
3-deoxyglucal (9), 4H5	C1	−0.213	0.180	0.013 (α)	neither (1:1)
	C2	−0.726	0.713	0.019 (α)
3-deoxyglucal (9), 5H4	C1	−0.169	0.214	0.017 (β)	”
	C2	−0.651	0.711	0.082 (β)
3-deoxyglucal, 4,6-acetal (8)	C1	−0.188	0.204	0.006 (β)	β (2:1)
	C2	−0.676	0.674	0.003 (α)
3-deoxygalactal (15)	C1	−0.217	0.183	0.013 (α)	α (>20:1)
	C2	−0.723	0.674	0.069 (α)
3-deoxygalactal, 4,6-acetal (14)	C1	−0.134	0.095	0.009 (α)	α (4:1)
	C2	−0.454	0.430	0.021 (α)
dideoxypentenoside	atom	cαb	cβ b	p c	expt e
2-deoxy-β-glc (20)	C5	−0.139	0.226	0.032 (β)	α (>20:1)
	C4	−0.391	0.182	0.120 (α)
2-deoxy-α-glc (21)	C5	−0.201	0.180	0.008 (α)	α (10:1)
	C4	−0.719	0.719	0.000
3-deoxy-β-glc (26), 2H1	C5	−0.221	0.172	0.019 (α)	β (3:2)
	C4	−0.679	0.690	0.015 (β)
3-deoxy-β-glc (26), 1H2	C5	−0.074	0.162	0.021 (β)	”
	C4	−0.477	0.457	0.018 (α)
3-deoxy-α-glc (27)	C5	−0.230	0.184	0.019 (α)	β (>20:1)
	C4	−0.639	0.691	0.069 (β)
D-xylal (28)	C1	−0.077	0.129	0.011 (β)	α (5:1)
	C2	−0.311	0.200	0.056 (α)
L-arabinal (29)	C1	−0.174	0.221	0.019 (α)	α (>20:1)
	C2	−0.709	0.753	0.064 (α)

^aAll structures optimized by DFT-B3LYP calculations (6–31+G(d,p)) using prior to insertion of s-functions. Unless otherwise stated, glycals and DDPs were optimized starting from their respective ⁴H₅ and ²H₁ conformations.

^bEach coefficient is calculated as the linear combination of s-function and 2py; +/− values refer to the sign of the coefficients for each lobe.

^cNet polarization of each orbital in parentheses.

^dα:β selectivities from Table 3.

^eα:β selectivities from Table 4.