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Башкирский Государственный Аграрный Университет

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Реакции N-алкил(арил)альд- и кетиминов с эфирами кислот фосфора. Монография

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N	R2		L MB		HNR2			NH2
N	R2		L MB		HNR2			NH2
		+ (MeO)2PHO	n
1		+ (MeO)2PHO	1			P(O)(OMe)2	1	P(O)(OMe)2
1			1				1
R H				R			R
						93

93, R1=Et, i-Pr, Me; R2=Tf, CHPh2, 4-MeOC6H4.

-1 2 1 (92-96% ), 1 Na-1 (49-55% ). + 2 -

1 . , 1

La B-1 1 1- . 4 -

1 1 La-1 1 1. " 1 1 1 1 1,

N-K- 1. 4 1

1 (93) 1 La B.

/ 1- 1 1 2

C=N 1 9 1 39 1,3- (94). /

1 2

Ln (Pr, Sm, Gd, Dy, Yb), M (K, Na), ((0,

, (0/ 1:7), 1 (R)-LnMB (5-20 1 %), 1 (-20°,, 1 1 50°,). , 1

1 (R)-YbPB-1 [67-69].

(R)-YbPB (5 1%)

(MeO)2P

+ (MeO)2PHO

50 0C, 48

(0/ 1:7

R1=H, R2=Me; R1=R2=Me; R1=Me, R2+R2=(CH2)5; R2=Me, R1+R1=(CH2)5

+ , 1 , (95)

79-88%, 2 – 87-95% . + [68]

, (R)-Ln B 1

1 1, 1 1 1 . 4 1 C=N ,

4- (95). 4-1

(95) 1 1 (R)- LnPB.

4 2 N-1 -

1 1 (85-91%) 2 (96-99% 9) 1 L/Me2Zn [70].

R=Ph, 4-MeC6H4, 4-MeOC6H4, 3-MeOC6H4, 2-FC6H4, 4-FC6H4, 4-

ClC6H4, 4-BrC6H4, 2- , -Hex.

	Ph		Ph
	Ph		Ph
Ph	OH	OH	Ph
		OH

		OH
L =	N		N

' 1

– Al(Salalen) 1 (96-97) [71-72], -

) Al(Salalen) 1:

				R
				N	t -Bu
				O
			Cl	Al
	N	N		O
	N	N		N	t - Bu
		Al		N	t - Bu
		Al
t-Bu	O	O	Bu-t
		Cl	97	R
			97	R
	Bu-t	t-Bu	R=H(a), Ph( ), Mesityl( ),		( )
		96

OMe

(10 1%) 96

OMe

(MeO) PHO

(0, 24

R P(O)(OMe)2

R=4-BrC6H4 (99%, 95% ), 4-ClC6H4 (95%, 95% ), 4-MeOC6H4 (92%, 85% ), 4-MeC6H4 (95%, 90% ), 2-MeC6H4 (93%, 87% ), 2- (91%, 84% ), 2- (99%, 69% )

N	X		97 ,			H NX
	+ (CF3CH2O)2PHO		97 ,
	+ (CF3CH2O)2PHO		1. 1.		Ph		P(O)(OCH2CF3)2
Ph	H		1. 1.		Ph		P(O)(OCH2CF3)2
					35-95%
N	P(O)Ph2	+ (CF3CH2O)2PHO		97 ,			NHP(O)Ph2
N

Ar	H					Ar	P(O)(OCH2CF3)2
Ar	H					Ar	P(O)(OCH2CF3)2

85-98% 88-98%

Ar=Ph(a), 4-ClC6H4( ), 4-BrC6H4( ), 4-NO2C6H4( ), 4-MeOC6H4( ), 4-MeC6H4( ), 3-MeOC6H4( ), 2-MeC6H4( ), 2- ( ), 2- ( )

, 1 1 (55-90%) α- -

(99)

( - )1 (tPcAlCl)

(98) 2 1 [73]

P(O)(OEt)2

HP(O)(OEt)2

=NNH-C

tPcAICI, 80 0C

NHNH-C

-H2O

R H2NHN

+ (101) (100),

[74].

X			tPcAlCl
			tPcAlCl

		N NHCOCH(R)NHBoc + (EtO)2PHO 80 0C, 20


	100

X NHNHCOCH(R)NHBoc

O=P(Et)2 101

101, R=Me, X=CH2 ( ), NBoc ( ); R=PhCH2, X=CH2 ( ),

R=CH2Ph, X=NBoc (. )

tPcAlCl - ( - )1

( 1 in situ N- -

1 (102) 1 [75].

			* *		(Me2N)2C=NH		*	O
			NH2	+ R1CHO			P	N R
			*		-H2O		*
			*				*
							102
(Me	N)	2	C=NH		* *	*
2		2
					NH	P(O)(OR2)	2
(R2O)2PHO					*	R1
						R1
					H
R1 =			O	S	N		; R2=Me, Et
R1 =			,	,	,	,	; R2=Me, Et
					N	N	N
						N
						H
						H

1 1

(103) 1 (104) [76-77]:

N+

t-Bu

R1R2N

Bu-t

B54

OCOBu-t

103, X= F( ), ArF ( )

104, R1=H, R2=Bn (a), R1=R2=Me ( )

) 1 1 2

R1	N		Ts	.103				R1
	N		Ts	.103			*= P
	P(O)H +							R2
	P(O)H +							R2
R2	R			-50oC, (0
R2							R	NHTs
								NHTs

R1=R2= -1, 2-CF C H , R=4-MeC					H , -2, 2- , t-Bu, -PhCH=CH, Ph;
	3	6	4	6		4

R1=Ph, R2= -1

(10 1 %) 103

R(OBn)P(O)H + PhCH=N

O=P

OBn

CH2Cl / 1:1

NHTs

-40 ,

82-92%

82-94% ee

R=2- ,)2, 4-CF3C6H4CH2, 4-MeC6H4CH2, -PhCH=CH

(10 1 %) 104

(R O)2P(O)

O)2PHO + R

CH= N

, 23 ,

R1=Ph, CF3CH2, ClCH2CH2,

NH Ph

2-NO2C6H4, 4-NO2C6H4,

R2=Ph, 3-

R =ClCH2CH2, R =Ph( ); 89%, 90%

R1=2-NO C H CH , R2=Ph( ), 99%, 93%

10 1% 104

(2-NO2C6H4CH2O)2PHO + RCH=N

(2-NO2C6H4CH2O)2P

Et2O

NHPh

R=Ph, 3- , i-Pr, c-Hex, t-Bu, 4-FC6H4, 4-MeOC6H4, 2-MeC6H4, 2-ClC6H4, 3-ClC6H4, 4-ClC6H4, 2- , 3- , 2- , 2- , 2- , 77-93%, 2-

– 81-99% .

– , , – 1-

2 1

2 1 1 1 [78-80]. +

2 -

+20º, (105)

, 2 , 1, 4668% . 4 20º, 2-

80% . 4 1 -

-20º, 1 ,

2 (88-94% ).

						NHBoc
	N	Boc	(10	1%)
	N	Boc

Ar			+ (EtO)2PHO		Ar	P(O)(OEt)2



						105

Ar=Ph, 1- , 2- , 3-MeC6H4, 4-MeC6H4, 2,5-Me2C6H3, 4-MeOC6H4, 3- , 2-ClC6H4

4 1 1: ,

, -

. " P(III) 1 1 -

1 , -

1.1.3 2 3 1 / %-,.

+ 1 1 -

1 1 « -

+ 0 , + 1 ( 11)». + -

1 1 NH-

, 1 1 ( 11) 1

1 1 1 CONH2 P(O)NH2,

P(O)H 1 1 – - -

. + 1

P(III) ( , - )

2 P(III), 1, - -

. * 1, 1 1 ,

α-1 . ! α- -

1 1. + «1 1 » -

1 in situ 1

1 1, 1 0 , 1 . +

0 ,, 1 1. , 1, 1, 1,

, α-

1 " 1. ) « » . '

1 1. (

3 1 1 1:

1.0 0 ,

, , 1 1 1, 1,

0 ,;

2.) 1 3

+ 1, 1, , -

1 3 1 1

. /

1, 0 ,. + ,

, 1 1

1 1 «1 1 1». + -

1 1

( ) N-H 1 ( ),

1 P(O)-H -

( ) 1 1 ( ).

+2 1 1 1 -

1 - ,

15 . * 1 1

1 .

. ) 1 1

1, 1, 1 1 1. - -

2 . ) 1 1 -

1 . 4

, 1 1 1.

1.1.3.1 /

+	23 1 , 1-
,	19 1 -
	1 1 1-

2 1. 1 1

1 75-80°, [81]. + 1-

80-94%.

75−80°C

R1R2C=O + R3NH2 + (EtO)2POH → R1R2C(NHR3)P(O)(OEt)2.

* 3 α- 1 (107) 1,

α-1 1 (106). -

[82-83].

1		Me				800C
1						800C
R CHO +		2 + (MeO)2PHO
R CHO +		2 + (MeO)2PHO
	NH2 R
	(S) - 106				MW -
R2		NH P(O)(OMe)	2	+		R2 NH P(O)(OMe)	2
			2				2

	Me R1					Me R1
	Me R1					Me R1
		(S, R) - 107				(S, S) - 107

(R,S)-107-1 3 1: -

, 1 R1 R2 64:36 – 93:07. 1 in situ 1 1

1 1 1

: re-face attack – 1

si-face attack . 4 -

1 (R,S)-1, 1 1 (S,S)-1:

				..
				Nu
				si
	R2	N		R1
		N		R1
(S, S) - 107	Me				(R, S) - 107
(S, S) - 107

1		H ..	H


		Nure
..
Nu = (MeO)2PHO		HOP(OMe)2

4 1 3 , 1, 6 1 1 R1. R1 = Ar, 1

64:36 – 78:20, R1 = t-Bu

82:18 – 91:09.

/ , 1 1 1 1 1, 1-

1, 1 1 1 1

1-1 1 1

1 . +

50-80°, 120 1 1 76-85%. + 1

1 1 1 2 1 1 98% 1

[84].

, 3 (109), 3 1

1, 1 1 , 1 (2-2) (108).

1 1 1 [85].

+ R2NH		+ (R3OCH	CH	O)	PHO	100 0C
	2

		2	2	2		MW
CHO		108				MW
CHO

			2
R1		NHR

P(OCH2CH2OR3)2

O109

R1=3,4,5-trimethoxy, H, 2-F, 4-F, 2-CF3, 3-CF3; R2=4-CF3C6H4,

6-MeO-benzothiazol-2-yl, 3-NO2C6H4; R3=Me, Et

) -

. + 3, 3 1

(111), 1 -

1 , 2-1-6-1-

1 (110). 1 4-5

1 1 1 12-15 1 [86].

			MeO	S
1		2	O)2PHO +	NH2
R	CHO + (R		O)2PHO +	N
				N
				110 H
		MeO		S
				NHCHR1P(O)(OR2)2
				N
				H
				111
1		,		2
R =			,	2
R =				4-HOC6H4-; R = OH	X
	S			4-HOC6H4-; R = OH	X
	S		N

X= Cl, Br, NO2

. 3

1 1

1 2 .

1 1 ,

1. +

70°, [87].

1, 3

1 (113 - ), 1 1 -

1 1 2 1, 11 1 1 1 1

[88].

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