Edit in JSFiddle

/** Used rotation code from https://github.com/shramov/leaflet-plugins/blob/master/layer/Marker.Rotate.js
As its not availabel on CDN
*/

/*
 * Based on comments by @runanet and @coomsie 
 * https://github.com/CloudMade/Leaflet/issues/386
 *
 * Wrapping function is needed to preserve L.Marker.update function
 */ (function () {
    var _old__setPos = L.Marker.prototype._setPos;
    L.Marker.include({
        _updateImg: function (i, a, s) {
            a = L.point(s).divideBy(2)._subtract(L.point(a));
            var transform = '';
            transform += ' translate(' + -a.x + 'px, ' + -a.y + 'px)';
            transform += ' rotate(' + this.options.iconAngle + 'deg)';
            transform += ' translate(' + a.x + 'px, ' + a.y + 'px)';
            i.style[L.DomUtil.TRANSFORM] += transform;
        },

        setIconAngle: function (iconAngle) {
            this.options.iconAngle = iconAngle;
            if (this._map) this.update();
        },

        _setPos: function (pos) {
            if (this._icon) this._icon.style[L.DomUtil.TRANSFORM] = '';
            if (this._shadow) this._shadow.style[L.DomUtil.TRANSFORM] = '';

            _old__setPos.apply(this, [pos]);

            if (this.options.iconAngle) {
                var defaultIcon = new L.Icon.Default;
                var a = this.options.icon.options.iconAnchor || defaultIcon.options.iconAnchor;
                var s = this.options.icon.options.iconSize || defaultIcon.options.iconSize;
                var i;
                if (this._icon) {
                    i = this._icon;
                    this._updateImg(i, a, s);
                }
                if (this._shadow) {
                    if (this.options.icon.options.shadowAnchor) a = this.options.icon.options.shadowAnchor;
                    s = this.options.icon.options.shadowSize;
                    i = this._shadow;
                    this._updateImg(i, a, s);
                }
            }
        }
    });
}());
//Rotation code ens here

//Arrow line code starts from here

var map = L.map('map').setView([21.1500, 79.0900], 5);

L.tileLayer('http://{s}.tile.openstreetmap.org/{z}/{x}/{y}.png', {
    attribution: '&copy; <a href="http://openstreetmap.org">OpenStreetMap</a> contributors, <a href="http://creativecommons.org/licenses/by-sa/2.0/">CC-BY-SA</a>',
    maxZoom: 18
}).addTo(map);

var coordinates = [
    [21.1500, 79.0900],
    [18.948932, 72.776714],
    [28.6139, 77.2090],
    [25.6000, 85.1000],
    [17.3700, 83.4800]
];

var arrowIcon = L.icon({
    iconUrl: 'data:image/png;base64,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',
    iconSize: [20, 20],
    iconAnchor: [10, 10],
    popupAnchor: [-3, -76]
});

for (var i = 1; i < coordinates.length; i++) {
    //Putting location marker
    L.marker(coordinates[i]).addTo(map);

	
    //Drawing simple line
    L.polyline([coordinates[0], coordinates[i]], {
        color: 'green'
    }).addTo(map);

    //Code for putting arrow with appropriate rotation
    var firstPoint = coordinates[0].slice(),
        secondPoint = coordinates[i].slice(),
        slope = ((secondPoint[1] - firstPoint[1]) / (secondPoint[0] - firstPoint[0])),
        angle = Math.atan(slope),
        rotation;
    
    //Shifting the graph Origin to point of start point
    secondPoint[0] = secondPoint[0] - firstPoint[0];
    secondPoint[1] = secondPoint[1] - firstPoint[1];
	
	//Fourth quadrant
    if (secondPoint[0] > 0 && secondPoint[1] < 0) {
        rotation = (angle * 180/Math.PI)/2;
    }
    //Second quadrant
    else if (secondPoint[0] < 0 && secondPoint[1] > 0) {
        rotation = 180 + (angle * 180/Math.PI);
    }
    //Third quadrant
    else if (secondPoint[0] < 0 && secondPoint[1] < 0) {
        rotation =  180 + (angle * 180/Math.PI);
    }
    //First quadrant
    else if (secondPoint[0] > 0 && secondPoint[1] > 0) {
        rotation = (angle * 180/Math.PI);
    }
	
	L.marker(coordinates[i], {icon: arrowIcon,iconAngle: rotation}).addTo(map);
};

<div id="map" style="width:100%;height:500px"></div>