An Investigation of the Enolization and Isomeric Products Distribution in the Water Promoted Aldol Reaction of Tropinone and Granatanone

Table 5

Calculated (B3LYP/6-31g(d) CPCM) reaction parameters for tropinone enol addition to aldehydes.

R^1	Reaction medium		Aldol isomer		HB-O		k(anti)/k(syn)		HB-O			K anti/syn HB–O		HB-N	K anti/syn HB–N	anti/syn
Ph	Gas/neat		exo,syn-3a		20.1		41.3		−2.0			133.9		−7.2	0.1	0.11
			exo,anti-3a		18.9				−4.9					−5.8
	Water		exo,syn-3a		20.7		15.2		−3.0			48.6		−8.3	0.7	0.69
			exo,anti-3a		19.1				−5.3					−8.1
p-NO2-C6H4	Gas/net		exo,syn-3b		17.8		14.4		−6.1			48.6		−10.9	0.2	0.28
			exo,anti-3b		16.2				−8.4					−10.0
	Water		exo,syn-3b		18.2		6.1		−6.5			29.3		−11.9	1.0	1.78
			exo,anti-3b		17.1				−8.5					−11.9
p-F-C6H4	Gas/neat		exo,syn-3c		21.3		31.3		−1.7			113.1		−6.7	0.1	0.25
			exo,anti-3c		19.3				−4.5					−5.5
	Water		exo,syn-3c		21.7		14.9		−2.0			48.6		−7.4	0.6	0.85
			exo,anti-3c		20.1				−4.3					−7.1
p-Cl-C6H4	Gas/neat		exo,syn-3d		20.1		21.3		−3.3			48.6		−8.1	0.1	0.16
			exo,anti-3d		18.3				−5.6					−6.8
	Water		exo,syn-3d		21.4		14.9		−2.8			41.1		−8.2	0.6	0.82
			exo,anti-3d		19.8				−5.0					−7.9
p-CF3-C6H4	Gas/neat		exo,syn-3e		18.9		40.2		−5.1			29.3		−9.3	0.2	0.20
			exo,anti-3e		16.7				−7.1					−8.3
	Water		exo,syn-3e		20.4		45.1		−4.2			24.7		−9.3	1.7	1.22
			exo,anti-3e		18.2				−6.1					−9.6
m-MeO-C6H4	Gas/neat		exo,syn-3f		20.3		46.2		−3.0			95.5		−8.0	0.1	0.11
			exo,anti-3f		18.1				−5.7					−6.8
	Water		exo,syn-3f		20.6		12.9		−3.3			41.1		−8.0	1.7	0.64
			exo,anti-3f		19.1				−5.5					−8.3
α-Naphth-	Gas/neat		exo,syn-3g		21.4		38.2		−1.0			311.5		−7.4	0.1	0.05
			exo,anti-3g		19.2				−4.4					−6.0
	Water		exo,syn-3g		21.8		8.3		−1.2			80.7		−7.9	0.5	0.49
			exo,anti-3g		20.5				−3.8					−7.5
p-MeO-C6H4	Gas/neat		exo,syn-3h		21.9		35.7		−0.4			96.5		−5.1	0.1	n.d.
			exo,anti-3h		19.8				−3.1					−3.9
	Water		exo,syn-3h		22.4		43.0		−0.8			65.7		−5.8	1.0	n.d.
			exo,anti-3h		20.2				−3.3					−5.8
MAD HBN															37.5