МСОС Лекции с поиском и закладками

1. OKMcneHMe MeTannaMM

1.3. npoM3BOAHbte cepe6pa

• OKMCb cepe6pa - Ag2 0 - MJUKHH 0KHC/IHTellb, npHMeHRIOT AJIR 0KHC/leHHR

a/lbAerHA0B H rHAP0XHH0H0B O	0
MeO
	OH
	2. HCI
HO	HO

• Kap6oHaT cepe6pa (Ag2 C03 /1.4e11HT ) MRrKHH 0KHC/IHTe/lb, npHMeHSIIOTA,IIR 0KHC/leHHR rMAP0KCHrpynn (naKTO/lbl > all > 2° > 1 °) B Kap60HH/lbHble C0eAMHeHMR (MeTOA <l>eTM30Ha)

	npeAnOnO>KMTenbHblM MexaHM3M OKMCneHMff
	R				l	RR
	H'o	H	'			H 0.;/	H.	0			0
	#
	•			•		Ago	Ago	R)lR
	•Ag	Ag
010						o o				D•Glc OH	6-flaKlOH OH
						')(
											OH
										0

OH

8OH

1. OKMCneHMe MeTannaMM

1.4. PeareHTbl Ha ocHoee pyreHHff Ru(VIII) - Ru04 - cHnbHblM oKMcnHre11b, npHMeHRfOT AJUI 0KMCneHHR <l>YHKL\MOHanbHblX rpynn, aneKeH0B, apoMaTMKM.

feHeHMpytoT «in situ» H3 RuCl3 HnM RuO2 {cat) + ReOx {eqv)/H2O-CCl4 - MeCN

ReOx: NalO41 NaCIO, K2S2O8

0

Ph•

Jl.

V

oH

0

75%

H

OMOM

Ru02

atlNal

4

H

OMOM

,,,,6

(c

0

,,,,6

Ac,.,

N

►

Ac,.,

N

CCl4/MeCN/H20

0

N .,,,,,/OH

N

,,,,,

I

98%

I

I

0+ Boe

Boe

OH

O

H

H

Ru02(cat)/Nal04

O

Ph

OH

i-,

Ph

CC14/MeCN/H20

72%

1. OKMcneHMe MerannaMM

1.4. PeareHTbl Ha OCHOBe pyreHMR Ru{VIII) - Ru04 _

	CCl4'MeCN/H2O	OH
		94%
Ph	1. RuCl3/NalO4
	(0,25eq) (55eq}
	CCl4'MeCN/H2O
Ph	►
	2.SOCl2/MeOH
Ph

35%

	N		1. RuCl,1cai Nal04		N
	\N				\N		1.CH20
		J	N			0
							...
				►			2. PBr
Cl	....-:0		CCl4'MeC /H20			0		3 CI
	Ph		2.SOCl2/MeOH Cl
					Ph

\
N	'(		N
	0	Br

Pti

H3 ►

Cl

',-:N,

;,;N

N

Ph

Annpo3011aM

1. OKMCneHMe MeTannaMH

1.5. PeareHTbl Ha OCHOBe OKCMAa OCMM.A Os(VIII)- 0S04 MflrKMM OKMCnMTenb, npMMeHJIIOT AJ'I.A AMrMAPOKCMnMpOBaHMJI anKeHOB

•peaKU.M.A CTepeoceneKTMBHa - CUH-npMCOeAMHeHHe

•KaTanM3MpyeTCSI 3° 0CH0BaHMSIMM (NEt3, Py, XMHYKnMAMH) M MsNH2

R1 R1

H+OH+ HO+H

H+OH HO+H

R2		R2
3pumpo- (Me3o)
R1		R1
_ Ho+H	+	H+OH
- H+aH	HO+H
R2	Tpeo	R2

• OsO4 A0por M BblC0K0T0KCM'feH, ml3T0MY B coepeMeHHblX eapMaHTax o6bl'fHO MCn0/lb3YtOT KaTaJ1MTM'feCKMe eapMaHTbl OSO4 cat. /ReOx eqv.

ReOx: NMO (AnA>t<OH), H2O2, K3 Fe(CN)6

1. OKMcneHMe MeTannaMM

1.5. PeareHTbl Ha OCHOBe OKCHAa OCMHR Os(VIII)

• peaKU.HR 3aMeAJ1ReTCR conpR>KeHHblMH 3A-rpynnaMH (KaTaJ1H3 Py, MsNH2)

		0	0		0	OMe
J--oMe	0s0 4	*OMe :H		H + HO		H
	Py			OH	HO	H
z		HO OH	H

• Ha/lH\fHe ranTO<l>HllbHblX {NH, OH) rpynn ycKOpReT AHrHAPOKCHllHpoeaHMe, AaBaff npM HaJlM\fMH aCMMMeTpH\feCKOro aTOMa 3pumpo-npOAYKT OTHOCMTeJlbHO HMet0114erocR u.eHrpa

			OH		(l
				AcHN--+--H
_o_s___ Yy
	40•►			HO	H
NHAc			OH NHAc	H	OH

1.5. PeareHTbl Ha ocHoee OKCMAa ocMMff Os{VIII)

• 0S04 cat. peaKL\Mff 00/IO>KeHa 6. WapnnecoM B OCHOBY acCMMeTpM"leCKOro

AMrMAPOKCMIIMpoeaHMff (AD), KaTa/lM3MpyeMaff XMpallbHblMM npOM3BOAHblMM XMHYKllMAMHa (XMHMH M XMHMAMH) - (DHQD)i PHAL M (DHQ)i PHAL

N::N

MeO

OMe

(DHQDhPHAL

• Ha OCHOBe 3TMX KaTa/1M3aTopoe pa3pa6oTaHbl KOMMep eCKM AOCTYnHble

peareHTbl AD-mixture

AD-mix- AD-mix-a

(DHQD)iPHAL	- 0.3%	(DHQhPHAL	"' 0.3°
K2OsO3(OH)4	- 0.05%	K2OsO3(OH)4	- 0.05%
ReOx: K3 Fe(CN)6	- 70%	ReOx: K3Fe(CN)6	- 70%
Bufer: K2CO3	-29.6'%	Bufer: K2CO3	-29.6%
13

1.5. PeareHTbl Ha OCHOBe OKCHAa OCMH Os(VIII)

OMe		OMe	OMe
Os04'NMO	N '--::::::
►		I
(DHQD)iPHAL

OEt	►2	OEt	1. TFA► (15-		0H	L_iA_IH			►co-OH
	AD-mix-aJMsNH					_	--l
	2								OH
0	t-BuOH/H 0	OH 0	2. EtOH/L\						s.
				OH					JleHn1rHH03"1H

OAc

0

Ph OMe

Os0 /NMO
4
-----	►►

(DHQbPHAL

	U
OH	O		►-
Ph Me
OH

BzHN	O
¥	U
Ph Me -....
	6H

BzHN	0
;	II	III••
O
Ph	O H

naKmnaKcon

[isl

Pa3Aen IV

MeTOAbl OKl/1ClleHll1f1

2. OK111cneH111e HeMeTann1111.1ecK111M111 peareHTaMM

2.OKMcneHHe HeMeTannH"leCKHMH peareHTaMM

2.1.OKMC/leHMe aKTMBMpoeaHHblM DMSO: npMMeHAtoTAJ1.A OKMC/leHMR

nepBtNHblX ·CR..PTOB B ant>AerHAbl M KeTOHbl.

AJI.A aKTM&al.lMM ,npMMeHAto P.RA MeKtp0ct,M11oa(E): A'20 (OJIAf>paKT-foJtAMaHL

TFAA, (C00)2 (WaepH), DCC (Mo<H>att), SOCl21 TsO

MexaHM3M OKMCJleHM.A:

HO

••

r .c,3

\5

-TsOH

-.

NEt3-,

BnQ...;,,-..· -

H

A«4CYOMSO

H

I

Et,N,CHA

UNrpal'lb

-78 -Cto r.,t

-0

0 1. U----::=-

·11,1s

HO

0

QyC

.... >--

-

H OMSO --o

I

2. OKMCneHMe HeMeTa/1nMl.feCKMMM peareHTaMM

• TpaHccl>opMaL\HH 030HHAOB

R2,R3=H

			1. TsOH
			2. NaHC03
			3.Me2S
	0	0
		I
MeOH/DCM	-78°C
		1. TsOH
Org. Synth. 1986, 64, 150		2.Ac20/NEt3

MeO

Me

0

OMe

MeO

OMe

0

0

H

0

Me