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Казанский национальный исследовательский технологический университет

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Химия

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Organic Reaction Mechanisms 1997

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K M#

	NO2
n		ButOK, THF
R	(11)
	(11)

(12)

n = 1, R = H n = 2, R = H

n = 3, RR = O(CH2)2O

ClCH2C CCH2OH

(11)

	O–			NO2

	+ N	O–
	+ N	O–
R	n	Cl	R	n
R		Cl	R
R	O		R	O
R			R

	(13)			(14)

% &#

# M

X	H	+	H
			+
H	X	H
(15)	(16)	(17)	(18)
X = H2O+


I			I
		–CH2Z			CH2Z
	I			CH2Z
(19)	(20)			(21)

		Z = COPh, COCMe3, or NO2
	TsO
		H		X
		H
					H
(22)					H
(22)			(23)
			(23)
			X = OH or OEt


		10
4O 5		9
4O 5		8			Et3SiH/TiCl4
3 O6 12				7 R′	Et3SiH/TiCl4

					CH2Cl2


2	O		1 O13		–78 °C
	O


			R

(24a)

i; R = R′ = CH3

ii; R = CH3, R′ = CH2Ph iii; R = R′ = H

N	N	Et2AlCl, RMgX
H		–80 to –90 °C

H (25)

OR′

O O

(24b)

(26)

MeO

				(CH2)n
MeO				OMe
				OMe
					OH


					H
		(27)
			n = 1,2
O	O	SR1
O	O

				E-Y
				Lewis acid

(29)

R1 = CH2CH3 X = H, Piv

CH2CF3

C6H4F

MeO

MeSO2Cl

(CH2)n

Et3N

MeO

CH2Cl2

(28)

E Y–

O +

SR1

(30)

(31)

R2 = alkyl, aryl, acyl

R2OH

Lewis acid

OR2

(32)

SiO2CAr

(35)

					OH	attack at
	O				OH	top face
						top face
					+
		ArCO2H			+
Si			Si		–O2CAr
Si		CHCl3	Si		–O2CAr
	(33)			(34)		attack at
	(33)			(34)		bottom face

Ar = p-nitrophenyl

OH O2CAr

(36)

	X	X
	O	O
5a	O	O
	O	O
O	6a	O
O		O
	(37)	(38)
		X = H or Cl

OR3

EtO2C

(39)

(40)

But O

But

silica

Si O

But

gel

3:1 mixture of

OH OH

diastereomers

63%

24%

(41)

(42)

(43)

J J

Acid

(44)

(45)

NuH

NsNH

(46)

(47)

R = Me, Ph

Ns = p-nitrobenzenesulfonyl

TsO		R2CuLi	R
	N		N
	Ts		Ts
	(48)		(49)

SiMe

But

F–

(50)

(51)

F3C

CH3

F3C

CH3

F3C

CH3

RLi

–78 °C – rt

(R = Me, Bu)

F3C

CF3

F3C CF3

F3C

CF3

(52)

retention

inversion

X = SMe, OMe, OCH2CH2NMe2

(53)

(54)

D3C

OEt CH3

S+ S

S BF4–

(55)

H+

(57)

k1/k2 ≈ 3

H+

(56)

HO–

HO N

N Me

H+

(58)

R2		R2	ZnR2Li			R2 R2
R2		R2				R2 R2
R2	endo	R2		exo			Zn(L)
			OTs		R1		R


R1		R1
R1		R1
(60)		(59)				(61)

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